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The gas-phase rotational spectrum from 8 to 750 GHz and the high-resolution infrared (IR) spectrum of pyridazine (o-C4H4N2) have been analyzed for the ground and four lowest-energy vibrationally excited states. A combined global fit of the rotational and IR data has been obtained using a sextic, centrifugally distorted-rotor Hamiltonian with Coriolis coupling between appropriate states. Coriolis coupling has been addressed in the two lowest-energy coupled dyads (ν16, ν13 and ν24, ν9). Utilizing the Coriolis coupling between the vibrational states of each dyad and the analysis of the IR spectrum for ν16 and ν9, we have determined precise band origins for each of these fundamental states: ν16 (B1) = 361.213 292 7 (17) cm−1, ν13 (A2) = 361.284 082 4 (17) cm−1, ν24 (B2) = 618.969 096 (26) cm−1, and ν9 (A1) = 664.723 378 4 (27) cm−1. Notably, the energy separation in the ν16-ν13 Coriolis-coupled dyad is one of the smallest spectroscopically measured energy separations between vibrational states: 2122.222 (72) MHz or 0.070 789 7 (24) cm−1. Despite ν13 being IR inactive and ν24 having an impractically low-intensity IR intensity, the band origins of all four vibrational states were measured, showcasing the power of combining the data provided by millimeter-wave and high-resolution IR spectra. Additionally, the spectra of pyridazine-dx isotopologues generated for a previous semi-experimental equilibrium structure (reSE) determination allowed us to analyze the two lowest-energy vibrational states of pyridazine for all nine pyridazine-dx isotopologues. Coriolis-coupling terms have been measured for analogous vibrational states across seven isotopologues, both enabling their comparison and providing a new benchmark for computational chemistry. [ABSTRACT FROM AUTHOR]

A high-resolution absorption spectrum of the S1–S0 transition of free-base phthalocyanine was observed and analyzed with improved reliability. The spectrum, with a partially resolved rotational structure, was obtained by using the buffer-gas cooling technique and a single-mode tunable laser. Our new analysis reveals that the S 1 ← S 0 0 0 0 band belongs to the a-type transition, where the electronic transition moment aligns parallel to the NH–HN direction, allowing the assignment of the S1 state to 1B3u. These results agree with a prior study using supersonic expansion and are well supported by theoretical calculations. Interestingly, the rotational constant B in the S1 state, which is often smaller than that in the ground state for typical molecules, was found to be slightly larger than that in the S01Ag state. This suggests a change in the character of π bonds with the electronic excitation. [ABSTRACT FROM AUTHOR]

It is important to understand the dynamics of red blood cells (RBCs) in blood flow. This requires the formulation of coarse-grained RBC models that reproduce the hydrodynamic properties of blood accurately. One of the models that successfully reproduces the rheology and morphology of blood has been proposed by Fedosov et al. [Comput. Methods Appl. Mech. Eng. 199, 1937–1948 (2010)]. The proposed RBC model contains several parameters whose values are determined by either various experiments or physical requirements. In this study, we developed a new method of determining parameter values precisely from the fluctuations of the RBC membrane. Specifically, we studied the relationship between the spectra of the fluctuations and model parameters. Characteristic peaks were observed in the spectra, whose peak frequencies were dependent on the parameter values. In addition, we investigated the spectra of the radius of gyration. We identified the peaks originating from the spring potential and the volume-conserving potential appearing in the spectra. These results lead to the precise experimental determination of the parameters used in the RBC model. [ABSTRACT FROM AUTHOR]

Computational analysis of difference spectra between two analogous systems is a challenging issue, as reliable estimation of a tiny difference spectrum requires an extraordinary precision of the two original spectra. We have developed an alternative new method to calculate the difference spectra under background-free conditions, which greatly improved the efficiency of computation. In this paper, we report further improvement by using efficient parallel implementation and the time correlation formula based on time derivative quantities. As a consequence, the present work achieved further remarkable acceleration in the calculations of difference infrared and Raman spectra in the order of magnitude and thereby allowed us by analyzing these difference spectra at a practical cost of computation. [ABSTRACT FROM AUTHOR]

The D5Π–X5Δ (0,0) band of vanadium hydride at 654 nm has been recorded by laser excitation spectroscopy and represents the first analyzed spectrum of VH in the gas phase. The molecules were generated using a hollow cathode discharge source, with laser-induced fluorescence detected via the D5Π–A5Π (0,0) transition. All five main (ΔΩ = ΔΛ) subbands were observed as well as several satellite ones, which together create a rather complex and overlapped spectrum covering the region 15 180–15 500 cm−1. The D5Π state displays the effects of three strong local perturbations, which are likely caused by interactions with high vibrational levels of the B5Σ− and c3Σ− states, identified in a previous multiconfigurational self-consistent field study by Koseki et al. [J. Phys. Chem. A 108, 4707 (2004)]. Molecular constants describing the X5Δ, A5Π, and D5Π states were determined in three separate least-squares fits using effective Hamiltonians written in a Hund's case (a) basis. The fine structure of the ground state is found to be consistent with its assignment as a σπ2δ, 5Δ electronic state. The fitted values of its first-order spin–orbit and rotational constants in the ground state are A = 36.5378 15 c m − 1 and B = 5.7579(13) cm−1, the latter of which yields a bond length of R 0 = 1.7212 2 Å. This experimental value is in good agreement with previous computational studies of the molecule and fits well within the overall trend of decreasing bond length across the series of 3d transition metal monohydrides. [ABSTRACT FROM AUTHOR]

The (sub-)millimeter wave spectrum of the non-rigid CH2OH radical is investigated both experimentally and theoretically. Ab initio calculations are carried out to quantitatively characterize its potential energy surface as a function of the two large amplitude ∠H1COH and ∠H2COH dihedral angles. It is shown that the radical displays a large amplitude torsional-like motion of its CH2 group with respect to the OH group. The rotation–torsion levels computed with the help of a 4D Hamiltonian accounting for this torsional-like motion and for the overall rotation exhibit a tunneling splitting, in agreement with recent experimental investigations, and a strong rotational dependence of this tunneling splitting on the rotational quantum number Ka due to the rotation–torsion Coriolis coupling. Based on an internal axis method approach, a fitting Hamiltonian accounting for tunneling effects and for the fine and hyperfine structure is built and applied to the fitting of the new (sub)-millimeter wave transitions measured in this work along with previously available high-resolution data. 778 frequencies and wavenumbers are reproduced with a unitless standard deviation of 0.79 using 27 parameters. The N = 0 tunneling splitting, which could not be determined unambiguously in the previous high-resolution investigations, is determined based on its rotational dependence. [ABSTRACT FROM AUTHOR]

In this paper, a novel methodology is presented for the construction of ab initio effective rotation–vibration spectroscopic models from potential energy and dipole moment surfaces. Non-empirical effective Hamiltonians are obtained via the block-diagonalization of selected variationally computed eigenvector matrices. For the first time, the derivation of an effective dipole moment is carried out in a systematic way. This general approach can be implemented quite easily in most of the variational computer codes and turns out to be a clear alternative to the rather involved Van Vleck perturbation method. Symmetry is exploited at all stages to translate first-principles calculations into a set of spectroscopic parameters to be further refined on experiment. We demonstrate on H2CO, PH3, CH4, C2H4, and SF6 that the proposed effective model can provide crucial information to spectroscopists within a very short time compared to empirical spectroscopic models. This approach brings a new insight into high-resolution spectrum analysis of polyatomic molecules and will be also of great help in the modeling of hot atmospheres where completeness is important. [ABSTRACT FROM AUTHOR]

Over the last decades, photoreceptive proteins were extensively studied with biophysical methods to gain a fundamental understanding of their working mechanisms and further guide the development of optogenetic tools. Time-resolved infrared (IR) spectroscopy is one of the key methods to access their functional non-equilibrium processes with high temporal resolution but has the major drawback that experimental data are usually highly complex. Linking the spectral response to specific molecular events is a major obstacle. Here, we investigate a cyanobacteriochrome photoreceptor with a combined approach of transient absorption spectroscopy in the visible and IR spectral regions. We obtain kinetic information in both spectral regions by analysis with two different fitting methods: global multiexponential fitting and lifetime analysis. We investigate the ground state dynamics that follow photoexcitation in both directions of the bi-stable photocycle (Pr* and Pg*) in the nanosecond and microsecond time regimes. We find two ground state intermediates associated with the decay of Pr* and four with Pg* and report the macroscopic time constants of their interconversions. One of these processes is assigned to a structural change in the protein backbone. [ABSTRACT FROM AUTHOR]

Sum frequency generation (SFG) spectroscopy has been established as a powerful interface probe technique based on the electric dipole approximation, while possible signals of quadrupole and bulk origin have also been known for a long time. In this work, we developed a computational tool, namely, Qsac (quadrupole susceptibility automatic calculator), to evaluate the comprehensive contributions of the dipole/quadrupole and interface/bulk in the arbitrary vibrational bands of SFG spectra. The calculations of relevant susceptibility terms are performed on the basis of the theory of energy representation using quantum chemical calculation and molecular dynamics simulation, which allows for semi-quantitative comparison among these terms on the same footing. We applied the Qsac to the methyl C—H stretching bands of organic molecules and found a general trend that the weak asymmetric bands are more sensitive to the bulk contribution than the symmetric ones. The phases of interface and bulk terms tend to cancel in the asymmetric band, which results in the reduced band intensity in the SFG spectra. [ABSTRACT FROM AUTHOR]

A laser vaporization cluster source is coupled to the Fourier-transform ion cyclotron resonance mass spectrometer beamline of the free-electron laser for intracavity experiments. Gas phase metal ions and their oxides (VO2+, NbO2+, and TaO2+) are formed and spectroscopically characterized using IR multiple-photon dissociation spectroscopy via loss of atomic oxygen and overcoming fragmentation energies of 3 eV–6 eV. The signal is observed for all MO2+ fundamental modes: the symmetric and anti-symmetric ν1 and ν3 stretch modes in the 900 cm−1–1000 cm−1 range and the ν2 bending mode in the 300 cm−1–450 cm−1 range. A remarkable substructure is observed for the bending vibration, which is at least partly due to the rovibrational substructure. [ABSTRACT FROM AUTHOR]

Here, we discuss the application, advantages, and potential pitfalls of using transient UV/Vis (ultraviolet-visible) absorption spectroscopy to study photoelectrodes for water splitting. We revisit one of the most commonly studied water oxidation photoanodes (α-Fe2O3−x) to provide commentary and guidelines on experiment design and data analysis for transient absorption (TA) studies of photoelectrodes within a photoelectrochemical cell. We also assess the applicability of such in situ TA studies to understand photoelectrodes under operating conditions. A major limitation is that most, if not all, past in situ TA studies have been carried out using only pulsed light sources to generate carriers, with the electrode held in the dark at other times, which is shown to be a poor model for operating conditions. However, with a simple modification of existing TA experiments, a simple operando TA measurement is reported. [ABSTRACT FROM AUTHOR]

We present a conspectus of recent joint spectroscopic and computational studies that provided novel insight into the photochemistry of hydrogen-bonded complexes of the heptazine (Hz) chromophore with hydroxylic substrate molecules (water and phenol). It was found that a functionalized derivative of Hz, tri-anisole-heptazine (TAHz), can photooxidize water and phenol in a homogeneous photochemical reaction. This allows the exploration of the basic mechanisms of the proton-coupled electron-transfer (PCET) process involved in the water photooxidation reaction in well-defined complexes of chemically tunable molecular chromophores with chemically tunable substrate molecules. The unique properties of the excited electronic states of the Hz molecule and derivatives thereof are highlighted. The potential energy landscape relevant for the PCET reaction has been characterized by judicious computational studies. These data provided the basis for the demonstration of rational laser control of PCET reactions in TAHz–phenol complexes by pump–push–probe spectroscopy, which sheds light on the branching mechanisms occurring by the interaction of nonreactive locally excited states of the chromophore with reactive intermolecular charge-transfer states. Extrapolating from these results, we propose a general scenario that unravels the complex photoinduced water-splitting reaction into simple sequential light-driven one-electron redox reactions followed by simple dark radical–radical recombination reactions. [ABSTRACT FROM AUTHOR]

Electronic spectra for the hypermetallic oxide MgOMg have been observed in the 21 100 cm−1–24 000 cm−1 spectral range using laser induced fluorescence and two-photon resonantly enhanced ionization techniques. Rotationally resolved data confirmed the prediction of a X ̃ 1 Σ g + ground state. The spectrum was highly congested due to the optical activity of a low-frequency bending mode and the presence of three isotopologues with significant natural abundances. Ab initio calculations predict a bent equilibrium structure for the à 1B2 upper state, consistent with the observation of a long progression of the bending vibration mode. However, the vibrational intervals were not reproduced by the theoretical calculations. In part, this discrepancy is attributed to strong vibronic coupling between multiple electronically excited states. Two-photon ionization measurements were used to determine an ionization energy of 6.5800(25) eV. [ABSTRACT FROM AUTHOR]

Quantum light is a key resource for promoting quantum technology. One such class of technology aims to improve the precision of optical measurements using engineered quantum states of light. In this study, we investigate transmission measurement of frequency-entangled broadband photon pairs generated via parametric down-conversion with a monochromatic laser. It is observed that state-to-state dynamics in the system under study are temporally resolved by adjusting the path difference between the entangled twin beams when the entanglement time is sufficiently short. The non-classical photon correlation enables time-resolved spectroscopy with monochromatic pumping. It is further demonstrated that the signal corresponds to the spectral information along anti-diagonal lines of, for example, two-dimensional Fourier-transformed photon-echo spectra. This correspondence inspires us to anticipate that more elaborately engineered photon states would broaden the availability of quantum light spectroscopy. [ABSTRACT FROM AUTHOR]

Development of noble metal nanostructure substrates that provide strong near-field enhancements enables applications of linear and nonlinear infrared (IR) spectroscopies to study minute sample quantities, such as nanometer thick films and molecular monolayers. Large near-field enhancements of the electric fields used for spectroscopic interrogation of molecules at the nanostructure surface result in enhancement of the spectroscopic signatures. This enhancement scales with the nonlinear order of the method, providing particularly large signal gains for third- and fifth-order IR methods, reaching 106 and 108 raw enhancement factors, not adjusted to the amount of interrogated sample. In this perspective, we overview the advances in the development of nano-arrays of antenna-like nanostructures for mid-IR measurements and illustrate their use in linear and especially nonlinear two-dimensional IR approaches. We discuss how studies of the interaction mechanisms between light, plasmonic antennas, and molecular excitations benefit from the nonlinear two-dimensional time-resolved methods, which involve high-order scaling of the signal with the excitation field, high sensitivity to signal localization, and coherence of the excitation over a broad bandwidth. On the other hand, we demonstrate how studies of molecular structure and ultrafast dynamics by these advanced spectroscopic methods benefit from surface enhancement of signals by plasmonic antennas. [ABSTRACT FROM AUTHOR]

The predissociation threshold of VO has been measured using resonant three-photon ionization (R3PI) spectroscopy. Given the high density of electronic states in the molecule, it is argued that the molecule dissociates rapidly as soon as the thermochemical bond dissociation energy (BDE) is exceeded, allowing the measured predissociation threshold to be assigned as the BDE. This is the first time a BDE has been measured using the R3PI method. The first photon is provided by an optical parametric oscillator (OPO) laser that promotes VO into a high-energy, discrete vibronic state. A tunable dye laser then excites the molecule further to a resonant state close to the dissociation limit where there is a quasi-continuum of states. A second photon from the same dye laser pulse ionizes the molecule, generating VO+ ions. The dye laser is then scanned to higher energies, and when the energy of one OPO photon plus one dye photon exceeds the BDE, the molecule dissociates before another dye photon can be absorbed to induce ionization. The combined photon energy at the sharp drop in the ion signal is assigned as the BDE. The experiment has been repeated using four different intermediate states, all yielding the same BDE, D0(VO) = 6.545(2) eV. Using thermochemical cycles, a revised value for the BDE of cationic VO is obtained, D0(V+–O) = 6.053(2) eV. The 0 K enthalpy of formation for VO(g) is also derived as Δ f H 0 K 0 VO (g) = 128.6(1.0) kJ mol−1. Previous spectroscopic and thermochemical studies of VO are reviewed. [ABSTRACT FROM AUTHOR]

Hyper-Raman (HR) spectra of polar liquids are reported. Acetone, acetonitrile, chloroform, and dimethyl sulfoxide in the liquid phase were measured by using a picosecond laser whose wavelength is 1064 nm and repetition rate is 200 kHz. HR spectra with a high signal to noise ratio were obtained without the surface enhancement or the electronic resonance effect. Due to the improvement of the sensitivity, many vibrational bands were first observed in HR spectroscopy. The peak frequencies, relative intensities, band assignments, including symmetry species, and depolarization ratios are examined. All IR active vibrational modes well separated were, indeed, observed in HR spectra following the selection rule, whereas HR spectra show not only similarity but also difference in relative signal intensities compared with IR spectra. This work demonstrates the possibility of HR spectra in the liquid phase and suggests further research on molecular structures by HR spectroscopy. [ABSTRACT FROM AUTHOR]

The strong inter-relationship between cyclohepta-1,3,5-triene (CHT) and norcaradiene (NCD) systems observed in some reactions has been extended to include the energy surfaces for some low-lying ionic states. Equilibrium structures for ionic states of CHT with 2A′ symmetry were routinely found; the structures emerging with 2A′′ symmetry were NCD ionic states. A detailed analysis of these surfaces as a function of the C1 to C6 distance showed that while minima occurred for both state symmetries, curve crossing occurs in CS symmetry, which is avoided by distortion to C1 symmetry. The CHT → NCD structural change is attributed to initial conrotatory closure of the singly occupied molecular orbital. A new synchrotron-based photoelectron spectrum (PES) for CHT up to 25 eV shows little vibrational structure. We have assigned the PES up to 17 eV using a variety of theoretical methods. The calculated lowest ionic state, X2A′, is predicted to have a very low vibrational frequency of 87 cm−1, leading to a high density of vibrational states. The Franck–Condon envelopes calculated for the two lowest states are almost completely contained within the envelope of the lowest PES band. A comparison of the predicted PES of CHT and NCD showed much closer agreement of the PES with that of CHT. An analysis of the 1H and 13C nuclear magnetic resonance (NMR) spectra of CHT showed no evidence of NCD. The increased chemical shifts arising from the higher frequencies used here lead to significant changes in appearance when compared with earlier NMR spectra. [ABSTRACT FROM AUTHOR]

Attenuated total reflectance Fourier transform infrared spectroscopy and sum frequency generation (SFG) vibrational spectroscopy have been employed to probe the molecular structure of N,N-dimethylformamide (DMF) and water mixture by varying the concentration of DMF. From the bulk studies, we observed a gradual decrease in the intensity with a continuous blue shift in the OH-stretch region with the increase in the DMF concentration. In contrast, no significant blue shift in the OH-stretch region is noticed from the SFG spectra collected from the air–aqueous binary mixture interface as a function of DMF concentration. However, the impact of DMF is found to be disruptive in nature toward the existing hydrogen bonding network of the pristine water at the interfacial region. Interestingly, in the CH-stretch region, the vibrational signatures of the DMF molecule show blue shifts, as proposed in earlier studies. We have calculated the molecular tilt angle of the methyl group of the DMF molecule as a function of DMF concentration. For the case of neat DMF, the observed tilt angle is ∼17.7° with respect to the surface normal. The value of tilt angle decreases with the decrease in DMF concentration and reaches a value of ∼1.7° for a mole fraction of 0.5, and it further increases with the decrease in DMF concentration. It achieves a value of ∼20° for the dilute DMF mole fraction of 0.05 in the binary mixture. This indicates that DMF molecules at the air–binary mixture interface are placing their methyl groups more toward the normal for the intermediate DMF concentrations. [ABSTRACT FROM AUTHOR]

Referencing schemes are commonly used in heterodyned spectroscopies to mitigate correlated baseline noise arising from shot-to-shot fluctuations of the local oscillator. Although successful, these methods rely on careful pixel-to-pixel matching between the two spectrographs. A recent scheme introduced by Feng et al. [Opt. Express 27(15), 20323–20346 (2019)] employed a correlation matrix to allow free mapping between dissimilar spectrographs, leading to the first demonstration of floor noise limited detection on a multichannel array used in heterodyned spectroscopy. In addition to their primary results using a second reference spectrometer, Feng et al. briefly demonstrated the flexibility of their method by referencing to same-array pixels at the two spectral edges (i.e., edge-pixel referencing). We present a comprehensive study of this approach, which we term edge-pixel referencing, including optimization of the approach, assessment of the performance, and determination of the effects of background responses. We show that, within some limitations, the distortions due to background signals will not affect the 2D IR line shape or amplitude and can be mitigated by band narrowing of the pump beams. We also show that the performance of edge-pixel referencing is comparable to that of referencing to a second spectrometer in terms of noise suppression and that the line shapes and amplitudes of the spectral features are, within the measurement error, identical. Altogether, these results demonstrate that edge-pixel referencing is a powerful approach for noise suppression in heterodyned spectroscopies, which requires no new hardware and, so, can be implemented as a software solution for anyone performing heterodyned spectroscopy with multichannel array detectors already. [ABSTRACT FROM AUTHOR]

We theoretically propose a spectroscopic method for measuring optically forbidden states using entangled two-photon absorption (TPA). As a model system, we consider a diatomic molecular system consisting of three adiabatic potentials, namely, ground, intermediate, and excited states, where the intermediate state cannot be directly excited from the ground state. In our method, we pump the excited state using entangled TPA and indirectly measure the optically forbidden intermediate state through the photon emission from the excited state to the intermediate state. The condition required for this method is only that the transition rate between the excited and intermediate states is sufficiently high. Using our proposed method, we show that the optically forbidden state can be detected with a high degree of accuracy when highly efficient and selective TPA is realized. [ABSTRACT FROM AUTHOR]

Surfaces and interfaces play important roles in many processes and reactions and are therefore intensively studied, often with the aim of obtaining molecular-level information from just the interfacial layer. Generally, only the first few molecular layers next to the interface are relevant for the surface processes. In the past decades, 2nd-order nonlinear spectroscopies including sum-frequency generation and second harmonic generation have developed into powerful tools for obtaining molecularly specific insights into the interfacial region. These approaches have contributed substantially to our understanding of a wide range of physical phenomena. However, along with their wide-ranging applications, it has been realized that the implied surface-specificity of these approaches may not always be warranted. Specifically, the bulk quadrupole contribution beyond the electric dipole-approximation for a system with a weak nonlinear interface signal, as well as the diffuse layer contribution at charged interfaces, could mask the surface information. In this perspective paper, we discuss the surface-specificity of 2nd-order nonlinear spectroscopy, especially considering these two contributions. [ABSTRACT FROM AUTHOR]

The growth dynamics of gold-silver core-shell (Au@Ag) nanoparticles are studied using in situ time-dependent second harmonic generation (SHG) and extinction spectroscopy to investigate the nanoparticle shell formation. The silver shell is grown by reduction of silver cations onto a 14 nm gold core using ascorbic acid in colloidal aqueous solution under varying reaction concentrations producing Au@Ag nanoparticles of final sizes ranging from 51 to 78 nm in diameter. The in situ extinction spectra show a rapid increase in intensity on the timescale of 5–6 s with blue shifting and narrowing of the plasmonic peak during the silver shell formation. The in situ SHG signals show an abrupt rise at early times of the reaction, followed by a time-dependent biexponential decrease, where the faster SHG lifetime corresponds to the timescale of the shell growth, and where the slower SHG lifetime is attributed to changes in the nanoparticle surface charge density. A large enhancement in the SHG signal at early stages of the reaction is caused by plasmonic hot spots due to the nanoparticle surface morphology, which becomes smoother as the reaction proceeds. The final extinction spectra are compared to finite-difference time-domain (FDTD) calculations, showing general agreement with experiment, where the plasmon peak red shifts and increases in spectral width as the silver shell thickness increases. These in situ SHG and extinction spectroscopy results, combined with FDTD calculations, help characterize the complicated processes involved in colloidal nanoparticle shell formation in real time for developing potential plasmon-enhanced nanomaterial applications. [ABSTRACT FROM AUTHOR]

A time-dependent (TD) formulation of equation-of-motion (EOM) coupled-cluster (CC) theory is developed, which, unlike other similar TD-EOM-CC approaches [D. R. Nascimento and A. E. DePrince III, J. Chem. Theory Comput. 12, 5834–5840 (2016)], can be applied to any type of linear electronic spectroscopy. The TD-EOM-CC method is formally equivalent to the standard frequency-domain formulation of EOM-CC theory, with a potential computational advantage of a comparatively low memory footprint. This general TD-EOM-CC framework is applied to the linear absorption and electric circular dichroism spectra of several small oxirane derivatives. [ABSTRACT FROM AUTHOR]

Methoxyphenols (MPs) are a significant component of biomass burning emissions which mainly exists in our atmosphere in the gas phase where they contribute to the formation of secondary organic aerosols (SOAs). Rovibrational spectroscopy is a promising tool to monitor atmospheric MPs and infer their role in SOA formation. In this study, we bring a new perspective on the rovibrational analysis of MP isomers by taking advantage of two complementary devices combining jet-cooled environments and absorption spectroscopy: the Jet-AILES and the SPIRALES setups. Based on Q-branch frequency positions measured in the Jet-AILES Fourier-transform infrared (FTIR) spectra and guided by quantum chemistry calculations, we propose an extended vibrational and conformational analysis of the different MP isomers in their fingerprint region. Some modes such as far-IR out-of-plane –OH bending or mid-IR in-plane –CH bending allow us to assign individually all the stable conformers. Finally, using the SPIRALES setup with three different external cavity quantum cascade laser sources centered on the 930–990 cm−1 and the 1580–1690 cm−1 ranges, it was possible to proceed to the rovibrational analysis of the ν18 ring in-plane bending mode of the MP meta isomer providing a set of reliable excited state parameters, which confirms the correct assignment of two conformers. Interestingly, the observation of broad Q-branches without visible P- and R-branches in the region of the C–C ring stretching bands was interpreted as being probably due to a vibrational perturbation. These results highlight the complementarity of broadband FTIR and narrowband laser spectroscopic techniques to reveal the vibrational conformational signatures of atmospheric compounds over a large infrared spectral range. [ABSTRACT FROM AUTHOR]

The millimeter/submillimeter spectrum of the CrBr radical has been recorded in the frequency range of 220–300 GHz using direct absorption techniques, utilizing a new instrumental design. This study is the first spectroscopic investigation of this radical species by any method. CrBr was synthesized in a DC discharge by the reaction of chromium vapor, produced in a Broida-type oven, with Br2CH2 in argon. Six to nine rotational transitions were measured for four isotopologues of this molecule in their natural abundances, 52Cr79Br, 52Cr81Br, 53Cr79Br, and 53Cr81Br. Each transition was found to consist of six distinct fine structure components, indicating a 6Σ+ ground electronic state, as observed for CrF and CrCl. Lines originating in the v = 1 and 2 vibrational states were recorded for 52Cr79Br and 52Cr81Br as well. The spectra were analyzed using a Hund's case (b) Hamiltonian, and rotational, spin-spin, and spin-rotation parameters were determined. The third-order spin-rotation constant γs and the fourth order spin-spin term θ were necessary for the analysis; these parameters are thought to play a role in states with high multiplicities. Equilibrium parameters were also derived for the CrBr; a bond length of re = 2.337 282 (30) Å and a vibrational constant of ωe ≅ 300 cm−1 were determined. The sign and magnitude of the spin-spin and spin-rotation constants suggest the presence of nearby 4Π and 6Π excited states in CrBr, lying ∼9000 cm−1 above the ground state. The new instrument design, employing more compact, free-space optics utilizing an offset ellipsoidal mirror, facilitated these measurements. [ABSTRACT FROM AUTHOR]

Rotational transitions of the mono(β)-deuterated vinyl radical, HDC=CH, produced in a supersonic jet expansion by the ArF excimer laser photolysis, were observed by millimeter-wave spectroscopy. The b-type rotational transitions together with the weak a-type transitions were observed only for the lower component of the tunneling doublet, and no tunneling-rotation transitions connecting the lower and upper components were observed, suggesting that state mixing between the two components is negligibly small. The derived molecular constants such as the A rotational constant, Fermi contact interaction constants, and magnetic dipolar interaction constants indicate that the carrier of the observed spectrum is the trans-form of HDC=CH isomers, where the α-proton is located on the opposite side of the β-deuteron. The present conclusion of the trans-form of HDC=CH was also supported by the ab initio calculation in the CCSD(T)/cc-pVTZ level since the trans-form is calculated to be located by 30.04 cm−1 lower than the cis-form due to the difference in the zero point energy. As a result, the tunneling components in the ground state of HDC=CH behave as two different isomers localized at the trans- and cis-wells of the asymmetric double minimum potential. Observed hyperfine constants for HDC=CH were compared with those for H2C=CH to be consistent with each other. [ABSTRACT FROM AUTHOR]

We study the near-threshold photodissociation dynamics of NO2 by a kinematically complete femtosecond pump-probe scheme using a cold target recoil ion momentum spectrometer. We excite NO2 to the optically bright A ̃ 2 B 2 state with a 400 nm pulse and probe the ensuing dynamics via strong field single and double ionization with a 25 fs, 800 nm pulse. The pump spectrum spans the NO(X2Π) + O(3P) dissociation channel threshold, and therefore, following internal conversion, excited NO2 is energetically prepared both "above threshold" (dissociating) and "below threshold" (nondissociating). Experimentally, we can clearly discriminate a weak two-photon pump channel from the dominant single-photon data. In the single ionization channel, we observe NO+ fragments with nonzero momentum at 200 fs delay and an increasing yield of NO+ fragments with near-zero momentum at 3.0 ps delay. For double ionization events, we observe a time-varying Coulombic kinetic energy release between the NO+ and O+ fragments impulsively created from the evolving "hot" neutral ground state. Supported by classical trajectory calculations, we assign the decreasing Coulombic kinetic energy release at longer time delays to the increasing average NO–O distances in the ground electronic state during its large amplitude phase space evolution toward free products. The time-resolved kinetic energy release in the double ionization channel probes the large amplitude ground state evolution from a strongly coupled "inner region" to a loosely coupled "outer region" where one O atom is on average much further away from the NO. Both the time evolution of the kinetic energy release and the NO+ angular distributions support our assignments. [ABSTRACT FROM AUTHOR]

Vibrationally resolved photoelectron spectroscopy of terthiophene, quaterthiophene, and quinquethiophene radical anions is presented. The increased spectral resolution afforded by the combination of slow photoelectron velocity-map imaging and ion cooling in a cryogenic ion trap allows the characterization of vibronic structures within the S0 and T1 states. Analysis of the spectra, aided by electronic structure calculations and Franck-Condon simulations, revealed evidence for significant contributions from kinetically trapped higher energy conformers in the anion-to-triplet transitions. Unlike the lowest energy structures, where all the thiophene linkers are in the trans configuration, these higher energy conformers contain at least one cis linker. We also found that the adiabatic Franck-Condon simulations drastically underestimated the intensities of some vibronic features in the singlet ground state spectra due to large geometry changes upon photodetachment and anharmonic couplings in the singlet state. [ABSTRACT FROM AUTHOR]

A new nonlinear optical scheme relying on sum-frequency mixing in a KBe2BO3F2 crystal has been used to generate intense, broadly tunable, narrow-bandwidth, coherent vacuum-ultraviolet (VUV) radiation beyond 16 eV by resonance-enhanced four-wave mixing in Ar. The VUV radiation was used to record high-resolution pulsed-field-ionization zero-kinetic-energy photoelectron spectra of the N2O+ A+ ← N2O X photoionizing transition in the wave-number range from 132 000 cm−1 to 135 000 cm−1. The rotational structure of almost all vibrational levels of the A+ state with vibrational term values up to 2700 cm−1 could be resolved, and improved values of the first two adiabatic ionization energies of N2O, corresponding to the formation of the X+2Π3/2(000) J+ = 3/2 and A+2Σ+(000) N+ = 0 levels of N2O+ from the X 1Σ+(000) J″ = 0 ground state [103 969.30(12) cm−1 and 132 197.70(12) cm−1, respectively], were derived. The rotational intensity distributions of the bands were found to depend strongly on the value of the vibrational angular momentum of the ionic levels. The vibrational structure is discussed in terms of previously reported effective-Hamiltonian analyses. [ABSTRACT FROM AUTHOR]

We present an experimental technique using orbital angular momentum (OAM) in a fundamental laser field to drive high harmonic generation (HHG). The mixing of beams with different OAM allows us to generate two laser foci tightly spaced which generate harmonics that interfere in the far field. Thus, this technique is an OAM based in situ HHG interferometric spectroscopic method. With this tool, we measure the phase and amplitude of the angle dependent multiorbital HHG emission in molecular nitrogen. [ABSTRACT FROM AUTHOR]

We investigate the nonlinear optical response of alpha-quartz with phase-sensitive vibrational sum frequency generation (SFG) spectroscopy. Phase and amplitude of the generated sum frequency signal are determined by a complex interplay between signal contributions from the surface and the bulk of the crystal with the experimental geometry, in particular, the quartz azimuth. By combining anisotropy measurements with spectral- and phase resolution in our SFG experiment, we study this interplay and show that we can quantitatively isolate and characterize the contributions from the surface and bulk of the crystal. The obtained optical constants in combination with the presented mathematical framework fully describe the nonlinear response and allow for a precise determination of the phase of the overall SFG signal of quartz for any experimental geometry. This knowledge is of particular relevance because quartz is commonly used as a reference in phase sensitive SFG experiments. In such studies, the surface contribution is typically neglected and a constant value for the phase of the sum frequency response is assumed. Our study shows that this assumption is not generally accurate by revealing the considerable impact that the surface contribution can have on the overall response of the crystal. [ABSTRACT FROM AUTHOR]

In continuation with Paper I [S. R. Reddy et al., J. Chem. Phys. 151, 054303 (2019)], the vibronic structure and dynamics of the 1 Σ u + electronic state of C15, C17, C19, and C21 chains in the coupled manifold of 1 Σ u + –1Πg–1Πu– 1 Σ g + electronic states have been investigated in this paper. The model vibronic Hamiltonian developed through extensive ab initio quantum chemistry calculations in Paper I is employed, and first principles nuclear dynamics calculations are carried out to obtain the photoabsorption band of the 1 Σ u + electronic state. Both time-independent and time-dependent quantum mechanical calculations are carried out to precisely locate the vibrational levels, assign them with the progression of vibrational modes, and elucidate the impact of both Renner-Teller and pseudo-Renner-Teller couplings on them. The nonradiative decay of the 1 Σ u + electronic state is studied, and it is found that the decay rate is comparable with the prediction made for them to be qualified as a carrier of diffuse interstellar bands in the literature. The theoretical results are found to be in good accord with the available experimental results. [ABSTRACT FROM AUTHOR]

Covariance spectroscopy signals based on the transmission of broadband stochastic probe light undergoing a nonlinear optical process with matter are studied. The resulting signal depends on intensity correlation functions of the probe pulse. Application is made to transient absorption and stimulated Raman signals, where an ultraviolet pump and a delayed stochastically modulated infrared or optical Raman probe are used for monitoring vibrational excitations. We show that the stochastic properties of light can be exploited to circumvent the limitations on the joint temporal and spectral resolution of the signal. We study a model system with a time-dependent frequency and show that the dynamical information can be fully extracted from the covariance signal. This information is heavily suppressed upon averaging of noisy signals and practically inaccessible in conventional stimulated Raman measurements. [ABSTRACT FROM AUTHOR]

We report on a new approach to ease the computational overhead of ab initio "on-the-fly" semiclassical dynamics simulations for vibrational spectroscopy. The well known bottleneck of such computations lies in the necessity to estimate the Hessian matrix for propagating the semiclassical pre-exponential factor at each step along the dynamics. The procedure proposed here is based on the creation of a dynamical database of Hessians and associated molecular geometries able to speed up calculations while preserving the accuracy of results at a satisfactory level. This new approach can be interfaced to both analytical potential energy surfaces and on-the-fly dynamics, allowing one to study even large systems previously not achievable. We present results obtained for semiclassical vibrational power spectra of methane, glycine, and N-acetyl-L-phenylalaninyl-L-methionine-amide, a molecule of biological interest made of 46 atoms. [ABSTRACT FROM AUTHOR]

We present molecular-frame measurements of the recombination dipole matrix element (RDME) in CO2, N2O, and carbonyl sulfide (OCS) molecules using high-harmonic spectroscopy. Both the amplitudes and phases of the RDMEs exhibit clear imprints of a two-center interference minimum, which moves in energy with the molecular alignment angle relative to the laser polarization. We find that whereas the angle dependence of this minimum is consistent with the molecular geometry in CO2 and N2O, it behaves very differently in OCS; in particular, the phase shift which accompanies the two-center minimum changes sign for different alignment angles. Our results suggest that two interfering structural features contribute to the OCS RDME, namely, (i) the geometrical two-center minimum and (ii) a Cooper-like, electronic-structure minimum associated with the sulfur end of the molecule. We compare our results to ab initio calculations using time-dependent density functional theory and present an empirical model that captures both the two-center and the Cooper-like interferences. We also show that the yield from unaligned samples of two-center molecules is, in general, reduced at high photon energies compared to aligned samples, due to the destructive interference between molecules with different alignments. [ABSTRACT FROM AUTHOR]

Curcumin (Cur) is a natural polyphenol with a wide spectrum of biological activities and appealing therapeutic potential. Herein, it has been delivered by electrospray ionization as gaseous protonated species, [Cur + H]+, and as a Cu(ii) complex, [Cu(Cur − H)]+, a promising antioxidant and radical scavenger. The gas phase structures were assayed by infrared multiple photon dissociation (IRMPD) spectroscopy in both the fingerprint (800–2000 cm−1) and hydrogen stretching (3100–3750 cm−1) ranges. Comparison between the experimental features and linear IR spectra of the lowest energy structures computed at the B3LYP/6-311+G(d,p) level reveals that bare [Cu(Cur − H)]+ exists in a fully planar and symmetric arrangement, where the metal interacts with the two oxygens of the syn-enolate functionality of deprotonated Cur and both OCH3 groups are engaged in H-bonding with the ortho OH. The effect of protonation on the energetic and geometric determinants of Cur has been explored as well, revealing that bare [Cur + H]+ may exist as a mixture of two close-lying isomers associated with the most stable binding motifs. The additional proton is bound to either the diketo or the keto-enol configuration of Cur, in a bent or nearly planar arrangement, respectively. [ABSTRACT FROM AUTHOR]

Rayleigh-Brillouin scattering spectra of CO2 were measured at pressures ranging from 0.5 to 4 bars and temperatures from 257 to 355 K using green laser light (wavelength 532 nm, scattering angle of 55.7°). These spectra were compared to two line shape models, which take the bulk viscosity as a parameter. One model applies to the kinetic regime, i.e., low pressures, while the second model uses the continuum, hydrodynamic approach and takes the rotational relaxation time as a parameter, which translates into the bulk viscosity. We do not find a significant dependence of the bulk viscosity with pressure or temperature. At pressures where both models apply, we find a consistent value of the ratio of bulk viscosity over shear viscosity ηb/ηs = 0.41 ± 0.10. This value is four orders of magnitude smaller than the common value that is based on the damping of ultrasound and signifies that in light scattering only relaxation of rotational modes matters, while vibrational modes remain "frozen." [ABSTRACT FROM AUTHOR]

Doubly resonant infrared-visible sum-frequency generation (DR-IVSFG) spectroscopy, encompassing coupled vibrational and electronic transitions, provides a powerful method to gain a deep understanding of nuclear motion in photoresponsive surface adsorbates and interfaces. Here, we use DR-IVSFG to elucidate the role of vibronic coupling in a surface-confined donor-acceptor substituted azobenzene. Our study reveals some unique features of DR-IVSFG that have not been previously reported. In particular, vibronic coupling resulted in prominent SFG signal enhancement of selective stretching modes that reveal electronic properties of coexisting photochromic isomers. Our analysis explores two concepts: (1) In partially isomerized azobenzene at the surface, coupling of the fundamental vibrations to the S0 → S1 transition is more prominent for the cis isomer due to symmetry breaking, whereas coupling to the S0 → S2 transition was dominant in the trans isomer. (2) A strong coupling between the fundamental vibrations and the valence π-electron density, promoted by the initial absorption of an infrared photon, may result in suppression of the intensity of the hot band vibronic transition. This may translate into a suppressed sum-frequency generation signal at sum frequency wavelengths resonant with the S0 → S2 transition of the trans isomer. The weaker coupling of the fundamental vibrations to the non-bonding electron density localized on the azo group can therefore produce detectable sum-frequency generation at the resonance wavelength of the weaker S0 → S1 transition in the cis form. These results are explained in the framework of a linear coupling model, involving both Franck-Condon and Herzberg-Teller coupling terms. Our theoretical analysis reveals the important role played by molecular conformation, orientation, and vibronic interference in DR-SFG spectroscopy. [ABSTRACT FROM AUTHOR]

We report an extension of the recently proposed 2nd order dynamic correlation dressed complete active space method [S. Pathak et al., J. Chem. Phys. 147, 234109 (2017)] to incorporate spin-dependent relativistic effects into the Hamiltonian. The result is an effective Hamiltonian that contains the effects of static correlation, dynamic correlation, and relativistic effects on an equal footing. All contributions necessary for the description of magnetic phenomena and electron paramagnetic resonance (EPR) spectroscopy, namely, spin-orbit coupling, magnetic hyperfine coupling, Zeeman interaction, and direct electronic spin-spin coupling, are incorporated. We also suggest a novel analysis of g-matrices and A-matrices based on the singular value decomposition, which can provide not only the magnitude but also the sign of the principal components and allows for a transparent decomposition into different physical contributions. The new method was tested for excitation energies of first-row transition metal ions as well as D-tensors and g-shifts of first-row transition metal complexes using minimal active spaces. It was observed that state-mixing effects are usually small in these cases and that the results are comparable to nondegenerate N-electron valence state perturbation theory (NEVPT2) in conjunction with quasi-degenerate perturbation theory (QDPT). Results on EPR parameters of pseudo-square-planar Cu(ii) complexes show that state-mixing with a ligand-to-metal-charge-transfer configuration greatly improves results compared with NEVPT2/QDPT but also demonstrate that future modifications of the 0th order Hamiltonian or more elaborate electron correlation treatments will be necessary in order to achieve better agreement with the experiment. [ABSTRACT FROM AUTHOR]

The radial distribution functions of liquid water are known to change significantly their shape upon hydrostatic compression from ambient conditions deep into the kbar pressure regime. It has been shown that despite their eye-catching changes, the fundamental locally tetrahedral fourfold H-bonding pattern that characterizes ambient water is preserved up to about 10 kbar (1 GPa), which is the stability limit of liquid water at 300 K. The observed increase in coordination number comes from pushing water molecules into the first coordination sphere without establishing an H-bond, resulting in roughly two such additional interstitial molecules at 10 kbar. THz spectroscopy has been firmly established as a powerful experimental technique to analyze H-bonding in aqueous solutions given that it directly probes the far-infrared lineshape and thus the prominent H-bond network mode around 180 cm−1. We, therefore, set out to assess pressure effects on the THz response of liquid water at 10 kbar in comparison to the 1 bar (0.1 MPa) reference, both at 300 K, with the aim to trace back the related lineshape changes to the structural level. To this end, we employ the instantaneous normal mode approximation to rigorously separate the H-bonding peak from the large background arising from the pronounced librational tail. By exactly decomposing the total molecular dynamics into hindered translations, hindered rotations, and intramolecular vibrations, we find that the H-bonding peak arises from translation–translation and translation–rotation correlations, which are successively decomposed down to the level of distinct local H-bond environments. Our utmost detailed analysis based on molecular pair classifications unveils that H-bonded double-donor water pairs contribute most to the THz response around 180 cm−1, whereas interstitial waters are negligible. Moreover, short double-donor H-bonds have their peak maximum significantly shifted toward higher frequencies with respect to such long H-bonds. In conjunction with an increasing relative population of these short H-bonds versus the long ones (while the population of other water pair classes is essentially pressure insensitive), this explains not only the blue-shift of the H-bonding peak by about 20–30 cm−1 in total from 1 bar to 10 kbar but also the filling of the shallow local minimum of the THz lineshape located in between the network peak and the red-wing of the librational band at 1 bar. Based on the changing populations as a function of pressure, we are also able to roughly estimate the pressure-dependence of the H-bond network mode and find that its pressure response and thus the blue-shifting are most pronounced at low kbar pressures. [ABSTRACT FROM AUTHOR]

Through a decomposition of the bath correlation function, the hierarchical equations of motion are extended to the Ohmic spin-boson model at zero temperature. For two typical cutoff functions of the bath spectral density, the rate kernel of spin dynamics is numerically extracted by a time-convolution equation of the average magnetic moment. A characteristic time is defined accordingly as the inverse of the zeroth-order moment of the rate kernel. For a given Kondo parameter in the incoherent regime, the time evolution of average magnetic moments gradually collapses onto a master curve after rescaling the time variable with the characteristic time. The rescaled spin dynamics is nearly independent of the cutoff frequency and the form of cutoff functions. For a given cutoff frequency, the characteristic time with the change of the Kondo parameter is fitted excellently as a function of the renormalized tunneling amplitude. Despite a significant difference in definition, our result is in good agreement with the characteristic time of the noninteracting blip approximation. [ABSTRACT FROM AUTHOR]

We investigate the structure of water at the interface of three long-chain alcohol monolayers differing in alkyl chain length through molecular dynamics simulations combined with modeling of vibrational sum-frequency generation (vSFG) spectra. The effects of alkyl chain parity on interfacial water are examined through extensive analysis of structural properties, hydrogen bonding motifs, and spectral features. Besides providing molecular-level insights into the structure of interfacial water, this study also demonstrates that, by enabling comparisons with experimental vSFG spectra, computational spectroscopy may be used to test and validate force fields commonly used in biomolecular simulations. The results presented here may serve as benchmarks for further investigations to characterize ice nucleation induced by alcohol monolayers. [ABSTRACT FROM AUTHOR]

Field and laboratory measurements indicate that atmospheric organic aerosol particles can be present in a highly viscous state. In contrast to liquid state particles, the gas phase equilibration to ambient relative humidity (RH) can be kinetically limited and governed by condensed phase diffusion. In water diffusion experiments on highly viscous single aerosol particles levitated in an electrodynamic balance, we observed a characteristic shift behavior of the Mie scattering resonances indicative of the changing radial structure of the particle, thus providing an experimental method to track the diffusion process inside the particle. Due to the plasticizing effect of water, theory predicts extremely steep, front-like water concentration gradients inside highly viscous particles exposed to a rapid increase in RH. The resulting quasi step-like concentration profile motivates the use of a simple core-shell model describing the morphology of the non-equilibrium particle during humidification. The particle growth and reduction of the shell refractive index can be observed experimentally as redshift and blueshift behavior of the Mie resonances, respectively. We can deduce the particle radius as well as a core-shell radius ratio from the measured shift pattern and Mie scattering calculations. Using both the growth information obtained from the Mie resonance redshift and thermodynamic equilibrium data, we can infer a comprehensive picture of the time evolution of the diffusion fronts in the framework of our core-shell model. The observed shift behavior of the Mie resonances provides direct evidence of very steep diffusion fronts caused by the plasticizing effect of water and a method to validate previous diffusivity measurements. [ABSTRACT FROM AUTHOR]

We investigate barrier-crossing processes corresponding to collective hydrogen-bond rearrangements in liquid water using Markov state modeling techniques. The analysis is based on trajectories from classical molecular dynamics simulations and accounts for the full dynamics of relative angular and separation coordinates of water clusters and requires no predefined hydrogen bond criterium. We account for the complete 12-dimensional conformational subspace of three water molecules and distinguish five well-separated slow dynamic processes with relaxation times in the picosecond range, followed by a quasi-continuum spectrum of faster modes. By analysis of the Markov eigenstates, these processes are shown to correspond to different collective interchanges of hydrogen-bond donors and acceptors. Using a projection onto hydrogen-bond states, we also analyze the switching of one hydrogen bond between two acceptor water molecules and derive the complete transition network. The most probable pathway corresponds to a direct switch without an intermediate, in agreement with previous studies. However, a considerable fraction of paths proceeds along alternative routes that involve different intermediate states with short-lived alternative hydrogen bonds or weakly bound states. [ABSTRACT FROM AUTHOR]

Dynamic single-molecule force spectroscopy (SMFS) is a powerful method to characterize the mechanical stability of biomolecules. We address the problem that the standard manner of reporting the extracted energy landscape parameters does not reveal the intrinsic statistical errors associated with them. This problem becomes particularly relevant when SMFS is used to compare two or more different molecular systems. Here, we propose two methods that allow for a straightforward test of statistical significance. We illustrate the power of the methods by applying them to the experimental results obtained for three dimeric coiled coils of different lengths. Both methods are general and may be applied to any problem involving the fit of models with two correlated parameters. [ABSTRACT FROM AUTHOR]

Temperature Programmed Desorption (TPD) spectroscopy was used to determine the binding energies of polycyclic aromatic hydrocarbons CnHm (22 ≤ n ≤ 60) with highly oriented pyrolytic graphite. These energies were then used to estimate the dispersive graphite interlayer cohesion by means of a refined extrapolation method proposed by Björk et al. This yields a cohesion energy of 44.0 ± 3.8 meV per carbon atom. We discuss some limits of the TPD-based approach and contrast our values with previous determinations of the interlayer cohesion energy of graphite. [ABSTRACT FROM AUTHOR]

Variationally computed infrared spectra in the range [0-5000] cm−1 are reported for the deuterated PH2D and PHD2 molecules from accurate potential energy and dipole moment surfaces initially derived for the major isotopologue PH3( C 3 v ). Energy level and line intensity calculations were performed by using a normal-mode model combined with isotopic and symmetry transformations for the H → D substitutions. Theoretical spectra were computed at 296 K up to Jmax = 30 and will be made available through the TheoReTS information system (http://theorets.univ-reims.fr, http://theorets.tsu.ru). For the very first time, ab initio intensity predictions of PH2D/PHD2 are in good qualitative agreement with the literature. This work will be useful for spectral intensity analysis for which accurate spectral intensity data are still missing. [ABSTRACT FROM AUTHOR]

The stable low energy states of the HPS and DPS molecules have been studied through multi-reference ab initio methods in conjunction with large atomic basis sets. Stable states for these species have been examined up to 7 eV above the ground state minimum. We found six stable electronic states that are mostly mono-configurational. These states may be involved in the photodynamics and photodissociation of this molecule. In particular, the 2 1A′ state presents two minima on the potential energy surface, one of them close to linear configuration. This state may be populated after the absorption of a visible photon from the ground state and gives rise to large amplitude motions that may eventually induce isomerization to electronically excited HSP. Moreover, we characterized these states spectroscopically to facilitate the assignment of the vibronic spectra of the HPS and DPS species. For these low-energy states, we thus computed vertical and adiabatic excitation energies, and for the stable ones, a full set of spectroscopic constants including harmonic frequencies and anharmonic vibrational, rotational, and centrifugal distortion constants. The calculated potential energy surfaces for these states have been used in a variational procedure to deduce the pattern of vibrational levels up to 4000 cm−1 above the corresponding vibrationless level. Our data may serve for the assignment of the IR and Vis spectra of HPS and DPS. [ABSTRACT FROM AUTHOR]

High-resolution rotationally resolved spectra of the N–H stretch vibrational mode (ν1) of jet-cooled ND3H+ ions are collected and analyzed in a sub-Doppler slit-jet infrared spectrometer. The isotopomeric ammonium ions are generated by proton transfer from H3+ to ND3 in a discharge of an ND3/H2 gas mixture, whereby the slit jet expansion cools the nascent ND3H+ ions into lower rotational states. Rotational assignments are confirmed by four-line combination differences that agree to within the spectrometer precision (9 MHz). Based on precision two-line ground-state combination differences and a symmetric top Hamiltonian, the B, DJ, and DJK rotational constants for the ground vibrational state of ND3H+ are determined with high precision for the first time. Approximate rotational constants for the ν1 excited state are also determined, with a band origin at 3316.8425(19) cm−1 and in remarkable (∼0.1 cm−1) agreement with high level anharmonic theoretical predictions by Guo and co-workers [J. Phys. Chem. A, 120, 2185 (2016)]. Our results allow us to predict several low-J pure rotational transitions of ND3H+, which we hope will support future studies of this important ion in laboratory and astronomical rotational spectroscopy. [ABSTRACT FROM AUTHOR]