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We have recently shown that homogeneous and heterogeneous kinetics can be distinguished by experiments that compare the evolution of the population of a state over two time intervals [E. van Veldhoven et al., ChemPhysChem 8, 1761 (2007)]. This paper elaborates on the analogy between these multiple population-period transient spectroscopy (MUPPETS) experiments and more familiar spectroscopies based on the evolution of coherences. Using a modified inverse-Laplace transform, a standard kinetics decay is re-expressed as a “rate spectrum.” A nonexponential decay creates a linewidth in this spectrum. Mechanisms for line broadening in rate spectra are compared to those for line broadening in frequency-domain spectra. Homogeneous and heterogeneous kinetics are defined precisely and are shown to be the counterparts of homogeneous and inhomogeneous line broadenings in frequency-domain spectra. Homogeneous line broadening mechanisms are further divided into equilibrium and nonequilibrium mechanisms, with equilibrium mechanisms more prevalent in frequency spectra and nonequilibrium mechanisms more prevalent in rate spectra. Spectral representations of two-dimensional MUPPETS experiments are developed that are equivalent to two-dimensional coherence spectroscopies. In particular, spectra equivalent to hole-burning and to correlation spectra are defined. Frequency-domain spectra are often modeled as an inhomogeneous distribution of identical homogeneous line shapes. A parallel homogeneous-heterogeneous model for kinetics is defined. Within this model, MUPPETS has sufficient information to completely separate the homogeneous and heterogeneous contributions to a nonexponential decay, even when the homogeneous contribution is nonexponential. [ABSTRACT FROM AUTHOR]

The diagonal linewidth in two-dimensional infrared spectra is often narrower than the distribution of transition frequencies. The width along the antidiagonal is broader than predicted by the lifetime broadening. These effects arise from time-dependent fluctuations of the transition frequencies. They can be accounted for with a semiclassical approach. For systems with many coupled vibrational modes, this approach, however, becomes computationally too demanding to be practically applicable. A time-averaging approximation was suggested for linear infrared absorption spectra. In this paper, we demonstrate that the averaging can be optimized to fit a broader scale of frequency fluctuations by using a Gaussian weight function instead of the originally proposed box function. We further generalize the time-averaging method to allow the simulation of two-dimensional infrared spectra and demonstrate the method on a simple system. The approximation delivers a large speed-up of the calculation without losing significant accuracy. [ABSTRACT FROM AUTHOR]

This paper describes a method for synthesizing spin rotations with arbitrary space dependence on a sample of noninteracting spin 12 by using nonselective radio frequency pulses and pulsed field gradients. This method is used to map out spatial distribution of inhomogeneous B0 field and to engineer a space dependent evolution of spins that cancels the space dependent phase spins acquire when precessing in an inhomogeneous magnetic field. The technique allows one to record high resolution spectra in inhomogeneous magnetic field by using only time varying linear gradients and rf fields and is expected to find applications in ex situ NMR. [ABSTRACT FROM AUTHOR]

In recent years, sum-frequency generation (SFG) has been used to investigate numerous interfaces including aqueous interfaces. A longstanding challenge to interpretation of the SFG results, along with the related aqueous-solution infrared and Raman spectra, is a lack of connection between features in the broad hydrogen-bonded region and molecular-level interactions or configurations. This paper reports results of a newly developed polarization analysis of the generated sum-frequency signal as a function of wavelength both to deconvolute spectral resonances and to characterize the dynamic polarization associated with the resonances. Operationally, the polarization angle of the generated sum frequency is determined by identifying the null angle. The technique is hence termed polarization-angle null analysis or PAN. PAN applied to ice is very powerful; it reveals that the hydrogen-bonded region of the basal face of ice Ih contains at least five oscillators, each with a distinct polarization. The dynamic polarizability of the longest wavelength oscillator is nearly entirely transverse (perpendicular to the surface normal, i.e., in the surface plane); in contrast, the shortest wavelength oscillator is almost entirely longitudinal (along the surface normal). [ABSTRACT FROM AUTHOR]

The satellite transitions acquired in real time by magic angle spinning (STARTMAS) NMR experiment combines a train of pulses with sample rotation at the magic angle to refocus the first- and second-order quadrupolar broadening of spin I=3/2 nuclei in a series of echoes, while allowing the isotropic chemical and quadrupolar shifts to evolve. The result is real-time isotropic NMR spectra at high spinning rates using conventional MAS equipment. In this paper we describe in detail how STARTMAS data can be acquired and processed with ease on commercial equipment. We also discuss the advantages and limitations of the approach and illustrate the discussion with numerical simulations and experimental data from four different powdered solids. [ABSTRACT FROM AUTHOR]

An analytical expression is found for the accurate ab initio potential energy curve of the fluorine molecule that has been determined in the preceding two papers. With it, the vibrational and rotational energy levels of F2 are calculated using the discrete variable representation. The comparison of this theoretical spectrum with the experimental spectrum, which had been measured earlier using high-resolution electronic spectroscopy, yields a mean absolute deviation of about 5 cm-1 over the 22 levels. The dissociation energy with respect to the lowest vibrational energy is calculated within 30 cm-1 of the experimental value of 12 953±8 cm-1. The reported agreement of the theoretical spectrum and dissociation energy with experiment is contingent upon the inclusion of the effects of core-generated electron correlation, spin-orbit coupling, and scalar relativity. The Dunham analysis [Phys. Rev. 41, 721 (1932)] of the spectrum is found to be very accurate. New values are given for the spectroscopic constants. [ABSTRACT FROM AUTHOR]

The acquisition of ideal powder line shapes remains a recurring challenge in solid-state wideline nuclear magnetic resonance (NMR). Certain species, particularly quadrupolar spins in sites associated with large electric field gradients, are difficult to excite uniformly and with good efficiencies. This paper discusses some of the opportunities that arise upon departing from standard spin-echo excitation approaches and switching to echo sequences that use low-power, frequency-swept radio frequency (rf) pulses instead. The reduced powers demanded by such swept rf fields allow one to excite spins in different crystallites efficiently and with orientation-independent pulse angles, while the large bandwidths of interest that are needed by the measurement can be covered, thanks to the use of broadband frequency sweeps. The fact that the spins’ evolution and ensuing dephasing starts at the beginning of such rf manipulation calls for the use of spin-echo sequences; a number of alternatives capable of providing the desired line shapes both in the frequency and in the time domains are introduced and experimentally demonstrated. Sensitivity- and lineshape-wise these experiments are competitive vis-à-vis current implementations of wideline quadrupolar NMR based on hard rf pulses; additional opportunities that may derive from these ideas are also briefly discussed. [ABSTRACT FROM AUTHOR]

In this paper we derive the relativistic two-component formulation of time-dependent current-density-functional theory. To arrive at a two-component current-density formulation we apply a Foldy-Wouthuysen-type transformation to the time-dependent four-component Dirac-Kohn-Sham equations of relativistic density-functional theory. The two-component Hamiltonian is obtained as a regular expansion which is gauge invariant at each order of approximation, and to zeroth order it represents the time-dependent version of the relativistic zeroth order regular Hamiltonian obtained by van Lenthe et al., for the ground state [J. Chem. Phys.99, 4597 (1993)]. The corresponding zeroth order regular expression for the density is unchanged, whereas the current-density operator now comprises a paramagnetic, a diamagnetic, and a spin contribution, similar to the Gordon decomposition of the Dirac four current. The zeroth order current density is directly related to the mean velocity corresponding to the zeroth order Hamiltonian. These density and current density operators satisfy the continuity equation. This zeroth order approximation is therefore consistent and physically realistic. By combining this formalism with the formulation of the linear response of solids within time-dependent current-density functional theory [Romaniello and de Boeij, Phys. Rev. B71, 155108 (2005)], we derive a method that can treat orbital and spin contributions to the response in a unified way. The effect of spin-orbit coupling can now be taken into account. As first test we apply the method to calculate the relativistic effects in the linear response of several metals and nonmetals to a macroscopic electric field. Treatment of spin-orbit coupling yields visible changes in the spectra: a smooth onset of the interband transitions in the absorption spectrum of Au, a sharp onset with peak at about 0.46 eV in the absorption spectrum of W, and a low-frequency doublet structure in the absorption spectra of ZnTe, CdTe, and HgTe in agreement with experimental results. [ABSTRACT FROM AUTHOR]

Angle-resolved photoelectron spectra from rotationally selected à 1Au state acetylene have been recorded using velocity-map imaging. Several Renner-Teller split vibrational bands have been observed and assigned, showing good agreement with previous zero kinetic energy photoelectron (ZEKE) work [S. T. Pratt, P. M. Dehmer, and J. L. Dehmer, J. Chem. Phys. 99, 6233 (1993); S.-J. Tang, Y.-C. Chou, J. J.-M. Lin, and Y.-C. Hsu, ibid. 125, 133201 (2006).] The extracted photoelectron angular distributions (PADs) corresponding to these bands show a strong dependence on the vibronic angular momentum projection quantum number K+. Subbands with odd K+ show PADs with maximum intensity along the polarization vector of the ionizing laser beam, while those with even K+ show PADs with maximum intensity perpendicular to this direction. Velocity-map images recorded at low photoelectron energies approach rotational resolution of the ion, and the evolution of the PADs with increasing rotational level prepared in the à 1Au state indicates the potential of a “complete” determination of the photoionization dynamics of the à 1Au state. This is further investigated in the following paper. [ABSTRACT FROM AUTHOR]

In this paper, the structure and spectroscopic parameters of the C5 cluster are determined using multiconfigurational quantum chemical methods as implemented in the MOLCAS software. A number of spectroscopic properties (band center positions, l-doubling parameters, and rotational constants) have been characterized. From the new results, the assignments of previous astrophysical observations [J. Goicoechea et al., Astrophys. J. 609, 225 (2004)] are discussed. A detailed exploration of the global potential energy surface confirms that C5 has a X 1Σg+ linear isomer of prominent stability and, at least, three minimum energy structures showing singlet electronic ground states. Two of them are cyclic and one has a nonplanar geometry. Vertical and adiabatic electronic transitions and vibrational spectroscopic parameters are determined for the most stable linear isomer using multiconfigurational second order perturbation theory (CASPT2) using an active space containing 12 valence orbitals with 12 active electrons and extended ANO-type basis sets. The infrared spectrum has been analyzed from an anharmonic force field derived form the local surface, determined from the energies of a grid of 1350 geometries. The force field includes four coupling terms. The CASPT2 band center position of the ν7(πu) anharmonic fundamental has been calculated to be at 102 cm-1, which validates the assignment to C5 of the pattern of bands centered at 102 cm-1 observed with the ISO telescope. [ABSTRACT FROM AUTHOR]

In this work we have analyzed spectral moments characterizing properties of the collisionally hyper-Rayleigh scattered light. This is a supplementary study undertaken in order to complete the series of our previously published papers on the collisional hyper-Rayleigh scattering spectral profiles. In order to evaluate the moments we have extended the theory so that it could embrace the (hyper)polarizabilities of higher rank. Using the expressions developed on the grounds of the theoretical principles and applying appropriate computational methods with ab initio hyperpolarizability values as an input, we have obtained desirable moment values for three diatomic noble gas systems: HeNe, HeAr, and NeAr, at several temperature points. The semiclassical and the quantum treatments have been taken into account, and the moments were calculated both from the sum rule method as well as from the spectral profiles. The results were compared and discussed. [ABSTRACT FROM AUTHOR]

The analysis by infrared spectroscopy of aqueous mixtures of NaI and CsCl was made in order to obtain information at the molecular level of the mixing of these two salts taken as model systems of strong electrolytes in water. In previous papers [J.-J. Max and C. Chapados, J. Chem. Phys. 115, 2664 (2001) and J.-J. Max et al., ibid. 126, 184507 (2007)] it was reported that a pure salt in water forms pairs of monoions to which are attached a fixed number of water molecules, giving solvated water species. Due to their interaction with the ion pairs, the solvated water molecules are strongly perturbed, modifying the IR water spectrum being monitored. After taking the IR spectrum of pure water, a small volume of NaI 2M was added and the IR spectrum taken. Then a small volume of CsCl 2M was added and a new IR spectrum taken. This procedure was repeated to obtain a series of 38 spectra in the 0.05M–0.83M concentration range. Factor analysis made on the series revealed the presence of three types of water: pure water and two salt solvated waters. The number of solvated water molecules on the two salts taken together is ten. Since NaI and CsCl have, respectively, 3.5 and 3.0 solvated water molecules, it was concluded that a reaction occurred in the solutions forming NaCl and CsI that have, respectively, five water molecules each for a total of ten. The analysis of the spectra of the orthogonal factors supports this attribution. These results provide additional proof of ion pairing in water. Furthermore, comparing the band displacements and intensity variations observed on the solvated water species to that of pure water indicates that the dielectric milieu surrounding the ion pairs is not constant. These results do not support the classical view of Debye-Hückel that considers that the ions are independent and the dielectric milieu constant. The present results give some in situ information on the reaction that goes on in “simple” electrolyte systems whose reactivity and molecular organization are still not completely mastered. [ABSTRACT FROM AUTHOR]

X-ray and neutron diffractions, vibrational spectroscopy, and x-ray Raman scattering and absorption experiments on water are often interpreted in terms of hydrogen bonding. To this end a number of geometric definitions of hydrogen bonding in water have been developed. While all definitions of hydrogen bonding are to some extent arbitrary, those involving one distance and one angle for a given water dimer are unnecessarily so. In this paper the authors develop a systematic procedure based on two-dimensional potentials of mean force for defining cutoffs for a given pair of distance and angular coordinates. They also develop an electronic structure-based definition of hydrogen bonding in liquid water, related to the electronic occupancy of the antibonding OH orbitals. This definition turns out to be reasonably compatible with one of the distance-angle geometric definitions. These two definitions lead to an estimate of the number of hydrogen bonds per molecule in liquid simple point charge/extended (SPC/E) water of between 3.2 and 3.4. They also used these and other hydrogen-bond definitions to examine the dynamics of local hydrogen-bond number fluctuations, finding an approximate long-time decay constant for SPC/E water of between 0.8 and 0.9 ps, which corresponds to the time scale for local structural relaxation. [ABSTRACT FROM AUTHOR]

A continuous wave distributed feedback diode laser operating in the near infrared at wavelengths close to 1650 nm has been used to measure the extinction of light by single aerosol particles. The technique of optical feedback cavity ring-down spectroscopy (CRDS) was used for measurement of CRDS events at a repetition rate of 1.25 kHz. This very high repetition rate enabled multiple measurements of the extinction of light by single aerosol particles for the first time and demonstrated the dependence of light scattering on the position of a particle within the laser beam. A model is proposed to explain quantitatively this phenomenon. The minimum detectable dimensionless extinction coefficient [variant_greek_epsilon]min was determined to be 3×10-6. Extinction values obtained for single spherical polymer beads from a monodisperse sample of particles of diameter of 4 μm are in near-quantitative agreement with the values calculated by the Mie scattering theory. The deviations from the Mie theory expected for measurement of extinction by CRDS using a continuous wave laser are discussed in the companion paper. [ABSTRACT FROM AUTHOR]

In this paper the authors compare 400 nm one-photon and 800 nm two-photon two-dimensional Fourier transform electronic spectra of the organic laser dye Coumarin 102 in methanol using collinear optical pulse sequences and phase cycling. Results from the two different experiments show differences in the photon echo peak positions and shapes, reflecting differences in the two-photon and one-photon selection rules. [ABSTRACT FROM AUTHOR]

Absorption spectra related to heterogeneous electron transfer are analyzed with the focus on direct charge transfer transition from the surface attached molecule into the semiconductor band states. The computations are based on a model of reduced dimensionality with a single intramolecular vibrational coordinate but a complete account for the continuum of conduction band states. The applicability of this model to perylene on TiO2 has been demonstrated in a series of earlier papers. Here, based on a time-dependent formulation, the absorbance is calculated with the inclusion of charge transfer excitations. A broad parameter set inspired by the perylene TiO2 systems is considered. In particular, the description generalizes the Fano effect to heterogeneous electron transfer reactions. Preliminary simulations of measured spectra are presented for perylene-catechol attached to TiO2. [ABSTRACT FROM AUTHOR]

The Raman spectra of a series of push-pull molecules containing probenzenoid or quinoid spacers which are substituted with 1,3-dithiol-2-ylidene as donor and dicyano-methylene or barbituric acid as acceptors have been analyzed. The experimental spectra have been assigned and interpreted according to density functional theory calculations. Correlations between the Raman spectra of the isolated spacers and of the substituted molecules have been done. Raman bands in the 1620–1560 cm-1 interval provide vibrational markers of the quinoid↔aromatic structural evolution. This finding is supported by a careful inspection of geometrical parameters, namely, bond length alteration data and particular bond distances. As a result, the peak positions and relative intensities of these Raman features can be used to evaluate the benzenoid character of the spacer as a function of the donor/acceptor substitution pattern. This paper shows that Raman spectroscopy is a powerful spectroscopic tool for the analysis of the conjugational properties (i.e., intramolecular donor→acceptor charge transfer) of new organic materials. [ABSTRACT FROM AUTHOR]

In this paper, it is demonstrated that a Lorentzian line shape is predicted for a resonance interacting with a bath of equally spaced levels, even in the sparse, low density of states limit, if one performs an inhomogeneous average over the position of the bath states relative to the bright state. The implication for the spectroscopy of molecules in helium nanodroplets and possibly other samples with a significant size distribution is that coupling of excitations to phonons can lead to Lorentzian shaped transitions entirely from inhomogeneous broadening with no population relaxation in the sample. [ABSTRACT FROM AUTHOR]

Although it is quite promising to compute the spectroscopic energies [say, ionization potential (IP)] via the traditional valence-universal multireference coupled cluster (VUMRCC) method based on the description of the complete model space being seriously plagued by the perennial intruder state problem, the eigenvalue independent partitioning (EIP) based VUMRCC (coined as EIP-MRCC) method is quite effective to predict the spectroscopic energies in an intruder-free manner. Hence, the EIP-MRCC method is suitable for generating both the principal IPs and the satellite IPs of the inner-valence region. An EIP strategy converts the nonlinear VUMRCC equations for M(m,n) dimensional model space of m hole and n particle to a non-Hermitian eigenproblem of larger dimension whose M(m,n) roots are only physically meaningful. To increase the quality of the computed energy differences in the sense of chemical accuracy and to locate the correct position of it in the spectrum, the inclusion of higher-body cluster operators on top of all the standard singles-doubles is not the only pivotal issue, the effect of the size of the basis set is also equally important. This paper illustrates these issues by calculating the principal and satellite IPs of HF and HCl molecules using various basis sets (viz., Dunning's cc-pVDZ, cc-pVTZ, and cc-pVQZ) via EIP-MRCC method with full inclusion of triples (abbreviated as EIP-MRCCSDT). The results seem quite encouraging in comparison with the experimental values. The controversial 2Π satellite at 28.67 eV of HCl of Svensson et al. [J. Chem. Phys. 89, 7193 (1988)] is also reported. [ABSTRACT FROM AUTHOR]

The vibrational energy dissipation processes of the electronic ground states of p-nitroaniline and N,N-dimethyl-p-nitroaniline have been studied by transient grating spectroscopy with subpicosecond laser pulses. The rise time of the acoustic signal produced by the energy dissipation process of the hot ground state molecule was monitored. The acoustic signal was analyzed by an equation including the acoustic damping. The solvent temperature rise times in various solvents have been determined. The acoustic signals of azulene in previous papers [Y. Kimura et al., J. Chem. Phys. 123, 054512 (2005); 123, 054513 (2005)] were also reanalyzed using this equation. The temperature rise times in all cases are longer than the vibrational energy relaxation times of the solutes determined by the transient absorption measurements. The difference is discussed in terms of the energy transfer pathways from the solute to the solvent. We concluded that both the hydrogen bonding between the solute and the solvent and the lower frequency modes of the solutes play important roles in determining the energy transfer pathway from the solute to the solvent. [ABSTRACT FROM AUTHOR]

In Paper I, we studied vibrational properties of normal bases, base derivatives, Watson-Crick base pairs, and multiple layer base pair stacks in the frequency range of 1400–1800 cm-1. However, typical IR absorption spectra of single- and double-stranded DNA have been measured in D2O solution. Consequently, the more relevant bases and base pairs are those with deuterium atoms in replacement with labile amino hydrogen atoms. Thus, we have carried out density functional theory vibrational analyses of properly deuterated bases, base pairs, and stacked base pair systems. In the frequency range of interest, both aromatic ring deformation modes and carbonyl stretching modes appear to be strongly IR active. Basis mode frequencies and vibrational coupling constants are newly determined and used to numerically simulate IR absorption spectra. It turns out that the hydration effects on vibrational spectra are important. The numerically simulated vibrational spectra are directly compared with experiments. Also, the 18O-isotope exchange effect on the poly(dG):poly(dC) spectrum is quantitatively described. The present calculation results will be used to further simulate two-dimensional IR photon echo spectra of DNA oligomers in the companion Paper III. [ABSTRACT FROM AUTHOR]

Laser photoelectron spectra have been obtained following the preparation of eight vibrational states in S1 toluene. For four of the vibrational states (up to ∼550 cm-1 excess energy) excitation and ionization with nanosecond laser pulses give rise to photoelectron spectra with well-resolved vibrational peaks. For the other states (>750 cm-1 excess energy) the photoelectron spectra show a loss of structure when nanosecond pulses are used, as a result of intramolecular dynamics [see Whiteside et al., J. Chem. Phys. 123, 204317 (2005), following paper]. A number of vibrational peaks in the photoelectron spectra are assigned, and we find that the common series of ion vibrational peaks observed following the ionization of p-fluorotoluene in various S1 vibrational states is not reproduced in toluene. [ABSTRACT FROM AUTHOR]

Multidimensional spectroscopy has the ability to provide great insight into the complex dynamics and time-resolved structure of liquids. Theoretically describing these experiments requires calculating the nonlinear-response function, which is a combination of quantum-mechanical time correlation functions (TCFs), making it extremely difficult to calculate. Recently, a new theory was presented in which the two-dimensional Raman quantum response function R(5)(t1,t2) was expressed with a two-time, computationally tractable, classical TCF. Writing the response function in terms of classical TCFs brings the full power of atomistically detailed molecular dynamics to the problem. In this paper, the new TCF theory is employed to calculate the fifth-order Raman response function for liquid xenon and investigate several of the polarization conditions for which experiments can be performed on an isotropic system. The theory is shown to reproduce line-shape characteristics predicted by earlier theoretical work. [ABSTRACT FROM AUTHOR]

A state-selected beam of hydroxyl radicals is generated using a pulsed discharge source and hexapole field. The OH radicals are characterized by resonance-enhanced multiphoton ionization (REMPI) spectroscopy via the nested D 2Σ- and 3 2Σ- Rydberg states. Simplified spectra are observed from the selected |MJ|=3/2 component of the upper Λ-doublet level of the lowest rotational state (J=3/2) in ground (v″=0) and excited (v″=1–3) vibrational levels of the OH X 2Π3/2 state. Two-photon transitions are observed to the D 2Σ-(v′=0–3) and 3 2Σ-(v′=0,1) vibronic levels, extending previous studies to higher vibrational levels of the Rydberg states. Spectroscopic constants are derived for the Rydberg states and compared with prior experimental studies. Complementary first-principle theoretical studies of the properties of the D 2Σ- and 3 2Σ- Rydberg states [see M. P. J. van der Loo and G. C. Groenenboom, J. Chem. Phys. 123, 074310 (2005), following paper] are used to interpret the experimental findings and examine the utility of the (2+1) REMPI scheme for sensitive detection of OH radicals. [ABSTRACT FROM AUTHOR]

Although the theories and potential applications of intermolecular multiple-quantum coherences (iMQCs) have been under active investigations for over a decade, discussion of iMQC NMR signal formation was mainly confined in the time domain. In this paper, a full line-shape theory was developed to describe iMQC signals in the frequency domain. Relevant features of the line shape, such as peak height, linewidth, and phase, were investigated in detail. Predictions based on the theory agree well with experimental and simulated results. Since radiation-damping effects always couple with iMQCs in highly polarized liquid-state NMR systems, and strongly radiation-damped signals have many spectral characteristics similar to those of iMQCs, a detailed comparison was also made between them from different spectral aspects. With detailed comparison of peak height, linewidth, and phase, this work demonstrates that the iMQC and radiation-damping phenomena result from two completely different physical mechanisms despite that both present similar signal features and coexist in highly polarized liquid-state NMR systems. [ABSTRACT FROM AUTHOR]

In this paper the structures of 4-aminophenol(H2O)1+ and 3-aminophenol(H2O)1+ clusters are investigated in molecular beam experiments by different IR/UV-double resonance techniques as well as the mass analyzed threshold ionization spectroscopy yielding both inter- and intramolecular vibrations of the ionic and neutral species. Possible structures are extensively calculated at the level of density functional theory (DFT) or at the ab initio level of theory. From the experimental and theoretical investigations it can be concluded that in the case of 4-aminophenol(H2O)1 one O[Single_Bond]H...O hydrogen-bonded structure exists in the neutral cluster but two structures containing either an O[Single_Bond]H...O or a N[Single_Bond]H...O hydrogen-bonded arrangement are observed in the spectra of the ionic species. This observation is a result of an intramolecular rearrangement reaction within the ion which can only take place if high excess energies are used. A reaction path via the CH bonds is calculated and explains the experimental observations. In the case of 3-aminophenol(H2O)1+ only one O[Single_Bond]H...O bound structure is observed both in the neutral and ionic species. Ab initio and DFT calculations show that due to geometrical and energetical reasons a rearrangement cannot be observed in the 3-aminophenol(H2O)1+ cluster ion. [ABSTRACT FROM AUTHOR]

All the pure rotational transitions reported in the previous studies [J. Chem. Phys. 113, 10121 (2000); J. Mol. Spectrosc. 222, 22 (2003)] and newly observed rotation-vibration transitions, P=1/2←3/2, for Ar–SH and Ar–SD [J. Chem. Phys. (2005), the preceding paper] have been simultaneously analyzed to determine a new intermolecular potential-energy surface of Ar–SH in the ground state. A Schrödinger equation considering the three-dimensional freedom of motion for an atom-diatom complex in the Jacobi coordinate, R, θ, and r, was numerically solved to obtain energies of the rovibrational levels using the discrete variable representation method. A three-dimensional potential-energy surface is determined by a least-squares fitting with initial values of the parameters for the potential obtained by ab initio calculations at the RCCSD(T)/aug-cc-pVTZ level of theory. The potential well reproduces all the observed data in the microwave and millimeter wave regions with parity doublings and hyperfine splittings. Several low-lying rovibrational energies are calculated using the new potential-energy surface. The dependence of the interaction energy between Ar and SH(2Πi) on the bond length of the SH monomer is discussed. [ABSTRACT FROM AUTHOR]

In the paper a combined experimental and theoretical investigation of the longitudinal optical phonon sidebands (PSBs) in the luminescence of free excitons in GaN at moderately high temperatures was reported. The spectral features, including line broadening, shift, and asymmetry of the one- and two-phonon PSBs, were revealed both experimentally and theoretically. It is found that the linewidth of the one-phonon PSB is surprisingly always larger than that of the two-phonon PSB in the interested temperature range. Moreover, the thermal broadening rates of the one- and two-phonon PSBs are considerably different. We adopted the Segall–Mahan theory [B. Segall and G. D. Mahan, Phys. Rev. 171, 935 (1968)] to compute the PSB spectra of the free excitons in GaN. Only one adjustable parameter, the effective mass of the holes, was used in the calculations. For the one-phonon PSB, an excellent agreement between theory and experiment is achieved when an adequate effective mass of the holes was used. [ABSTRACT FROM AUTHOR]

The theoretical principles underpinning the calculation of infrared spectra for condensed-phase systems in the context of ab initio molecular dynamics have been recently developed in literature. At present, most ab initio molecular dynamics calculations are restricted to relatively small systems and short simulation times. In this paper we devise a method that allows well-converged results for infrared spectra from ab initio molecular dynamics simulations using small systems and short trajectories characteristic of simulations typically performed in practice. We demonstrate the utility of our approach by computing the imaginary part of the dielectric constant [variant_greek_epsilon]″(ω) for H2O and D2O in solid and liquid phases and show that it compares well with experimental data. We further demonstrate that maximally localized Wannier orbitals can be used to separate the individual contributions of different molecular species to the linear spectrum of complex systems. The new spectral decomposition method is shown to be useful in present-day ab initio molecular dynamics calculations to compute the magnitude of the “continuous absorption” generated by excess protons in aqueous solutions with good accuracy even when other species present in the solutions absorb strongly in the same frequency window. [ABSTRACT FROM AUTHOR]

In this paper we present theoretical analyses on an infrared (IR) spectrum of amorphous selenium. The system is described by a 216-atom-chain model, and a set of molecular-dynamics simulations is performed to generate vitreous structures and vibrational modes. To describe an electronic structure of the system we employ a complete neglect of differential overlap model parametrized by ab initio cluster calculations. An IR intensity is evaluated with the Berry-phase formula for an electronic polarization. The effect of the through-space electron transfer on the IR spectrum is studied by artificially changing the magnitude of matrix elements associated with the electron transfer between nonbonded atoms in the chain. We find that the through-space electron transfer leads to (i) the enhancement of the bending IR peak at 135 cm-1 and (ii) the appearance of a new low-frequency peak around 50 cm-1, thus resulting in a good agreement with the experiment. The mechanism is discussed by a simple dipole model. [ABSTRACT FROM AUTHOR]

In this paper, we present a new analytical approach for describing the spin dynamics of synchronous and asynchronous time-dependent modulations in solid-state nuclear magnetic resonance experiments. The approach, based on multimode Floquet theory, employs the multipole operator basis of Sanctuary for spin description and illustrates the time evolution in the Floquet–Liouville space using the effective Hamiltonians obtained from the contact (or van Vleck) transformation procedure. Since the Hamiltonian and the density operator are expressed in terms of irreducible tensor operators, extensions to higher spin magnitudes (I>1/2) and multiple spins are quite straightforward and permit analytical treatments for many problems. We outline the general underlying principles involved in this approach with a brief mention of its potential application in other branches of spectroscopy. [ABSTRACT FROM AUTHOR]

In polar fluids such as water and methanol, the peak of the solvated electron’s absorption spectrum in the red has been assigned as a sum of transitions between an s-like ground state and three nearly degenerate p-like excited states bound in a quasispherical cavity. In contrast, in weakly polar solvents such as tetrahydrofuran (THF), the solvated electron has an absorption spectrum that peaks in the mid-infrared, but no definitive assignment has been offered about the origins of the spectrum or the underlying structure. In this paper, we present the results of adiabatic mixed quantum/classical molecular dynamic simulations of the solvated electron in THF, and provide a detailed explanation of the THF-solvated electron’s absorption spectrum and electronic structure. Using a classical solvent model and a fully quantum mechanical excess electron, our simulations show that although the ground and first excited states are bound in a quasispherical cavity, a multitude of other, nearby solvent cavities support numerous, nearly degenerate, bound excited states that have little Franck–Condon overlap with the ground state. We show that these solvent cavities, which are partially polarized so that they act as electron trapping sites, are an inherent property of the way THF molecules pack in the liquid. The absorption spectrum is thus assigned to a sum of bound-to-bound transitions between a localized ground state and multiple disjoint excited states scattered throughout the fluid. Furthermore, we find that the usual spherical harmonic labels (e.g., s-like, p-like) are not good descriptors of the excited-state wave functions of the solvated electron in THF. Our observation of multiple disjoint excited states is consistent with femtosecond pump-probe experiments in the literature that suggest that photoexcitation of solvated electrons in THF causes them to relocalize into solvent cavities far from where they originated. [ABSTRACT FROM AUTHOR]

We present data obtained by time-resolved terahertz spectroscopy in selected semiconducting and molecular systems exhibiting subpicosecond far-infrared dynamics. We use a frequency-domain method which eliminates the influence of instrumental functions and artifacts due to frequency mixing and yields a two-dimensional transient conductivity of the photoexcited sample. This technique enables improving the attainable experimental time resolution and allows a simple qualitative interpretation of the results without a priori modeling. The quantitative interpretation is based on the time-dependent Drude and damped harmonic oscillator models. [ABSTRACT FROM AUTHOR]

In experiments involving decaying signals, it is often desirable to analyze the data as a sum of exponential decays using the Laplace inversion method. However, Laplace inversion is an ill-conditioned problem, and it is difficult to ascertain the stability of the reconstruction method and resolution of the resulting spectrum. This paper provides an easily computed approximate bound of the resolution and offers guidelines on how to design experiments to improve the spectral resolution. [ABSTRACT FROM AUTHOR]

In this paper, I consider the Bethe and Thomas–Reiche–Kuhn sum rules, which together form the foundation of Bethe’s theory of energy loss from fast charged particles to matter. For nonrelativistic target systems, the use of closure leads directly to simple expressions for these quantities. In the case of relativistic systems, on the other hand, the calculation of sum rules is fraught with difficulties. Various perturbative approaches have been used over the years to obtain relativistic corrections, but these methods fail badly when the system in question is very strongly bound. Here, I present an approach that leads to relatively simple expressions yielding accurate sums, even for highly relativistic many-electron systems. I also offer an explanation for the difference between relativistic and nonrelativistic sum rules in terms of the Zitterbewegung of the electrons. [ABSTRACT FROM AUTHOR]

In this paper we derive the basic physics underlying infrared-x-ray pump-probe spectroscopy (IR, infrared). Particular features of the spectroscopy are highlighted and discussed, such as dependence on phase of the infrared pulse, duration and delay time of the x-ray pulse, and molecular orientation. Numerical applications are carried out for the water dimer using wave packet techniques. It is shown that core ionization of the donor oxygen of the water dimer results in a drastic change of the potential with the global minimum placed in the proton transfer region. The results of the modeling indicate that IR-x-ray pump-probe spectroscopy can be used to study the dynamics of proton transfer in this core-ionized state, and that, contrary to conventional core level photoelectron spectroscopy, x-ray core-ionization driven by an IR field is a proper method to explore the proton transfer in a system like the water dimer. We observe that the trajectory of the nuclear wave packet in the ground state potential well is strongly affected by the absolute phase of the IR pulse. [ABSTRACT FROM AUTHOR]

Infrared spectra of weakly bound hydrogen–krypton complexes have been studied at high spectral resolution (0.04 cm-1) using a long-path (154 m) low temperature (100 K) absorption cell and a Fourier transform spectrometer. In addition to spectra from the regions of the H2 and D2 fundamental vibrational bands in the midinfrared, the results also include the region of the pure rotational S0(0) transition of H2 in the far infrared. A total of 219 measured line positions from these spectra have been fully assigned to specific quantum transitions and form the basis for determining a greatly improved semiempirical three-dimensional intermolecular potential energy surface for hydrogen–krypton in an accompanying paper. [ABSTRACT FROM AUTHOR]

The temporal behavior of optical response functions (ORFs) reflects the quantum dynamics of an electronic superposition state, and as such lacks a well-defined classical limit. In this paper, we consider the importance of accounting for the quantum nature of the dynamics when calculating ORFs of different types. To this end, we calculated the ORFs associated with the linear absorption spectrum and the nonlinear two-pulse photon-echo experiment, via the following approaches: (1) the semiclassical forward-backward approach; (2) an approach based on linearizing the path-integral forward-backward action in terms of the difference between the forward and backward paths; (3) an approach based on ground state nuclear dynamics. The calculations were performed on a model that consists of a two-state chromophore solvated in a nonpolar liquid. The different methods were found to yield very similar results for the absorption spectrum and “diagonal” two-pulse photon echo (i.e., the homodyne-detected signal at time t=t0 after the second pulse, where t0 is the time interval between the two pulses). The different approximations yielded somewhat different results in the case of the time-integrated photon-echo signal. The reasons for the similarity between the predictions of different approximations are also discussed [ABSTRACT FROM AUTHOR]

The midinfrared (MIR) spectra of molecules in polar solvents exhibit inhomogeneously broadened bands whose spectral positions are shifted as compared to the gas phase. The shifts are caused by interactions with structured solvation shells and the broadenings by fluctuations of these interactions. The MIR spectra can be calculated from hybrid molecular dynamics (MD) simulations, which treat the solute molecule by density functional theory and the solvent by molecular mechanics by the so-called instantaneous normal mode analysis (INMA) or by Fourier transforming the time correlation function (FTTCF) of the molecular dipole moment. In Paper I of this work [M. Schmitz and P. Tavan, J. Chem. Phys. 121, 12233 (2004)] we explored an alternative method based on generalized virial (GV) frequencies noting, however, that GV systematically underestimates frequencies. As shown by us these artifacts are caused by solvent-induced fluctuations of the (i) equilibrium geometry, (ii) force constants, and (iii) normal mode directions as well as by (iv) diagonal and (v) off-diagonal anharmonicities. Here we now show, by analyzing the time scales of fluctuations and sample MD trajectories of formaldehyde in the gas phase and in water, that all these sources of computational artifacts can be made visible by a Fourier analysis of the normal coordinates. Correspondingly, the error sources (i) and (iii)–(v) can be removed by bandpass filtering, as long as the spectral signatures of the respective effects are well separated from the fundamental band. Furthermore, the artifacts arising from effect (ii) can be strongly diminished by a time-resolved version of the GV approach (TF-GV). The TF-GV method then yields for each mode j a trajectory of the vibrational frequency ωj(t|τ) at a time resolution τ>τj, which is only limited by the corresponding oscillation time τj=2π/ωj and, thus, is in the femtosecond range. A correlation analysis of these trajectories clearly separates the librational motions from the conformational dynamics of the solvation shells and yields the inhomogeneously broadened MIR spectra, if the theory of motional narrowing is properly included. The MIR spectrum of formaldehyde in solution obtained by TF-GV agrees very well with the FTTCF result, if one applies the so-called “harmonic approximation” quantum correction factor and a temperature scaling to the FTTCF intensities. Also for INMA an excellent agreement is achieved if one disregards a slight INMA overestimate of linewidths.© 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Recently an inorganic fullerine-like [As@Ni12@As20]3- onion with near-perfect icosahedral symmetry in the crystalline phase was reported [M. J. Moses, J. C. Fettinger, and B. W. Eichhorn, Science 300, 778 (2003)]. This paper presents a detailed computational study in the framework of density functional theory on various aspects of this molecule. The electronic structure of the As@Ni12@As20 is investigated in its neutral as well as -3 charged state together with its subunits As20 and As@Ni12 by the all electron linear combination of Gaussian-type orbitals method. The bonding is studied by examining the integrated charge within atomic sphere, the electron localization function, changes in the electron density distribution, and from vibrational modes. We find that strong covalent As-As bonds seen in isolated As20 become weaker in the As@Ni12@As20 and strong covalent As-Ni bonds are formed. The structural stability of all four clusters is examined by analyzing the energetics and by calculating the vibrational frequencies. Further, the infrared and Raman spectra is predicted for both the neutral and charged As@Ni12@As20 clusters. Finally, the energy barrier for removal of a single arsenic atom is calculated for the neutral As@Ni12@As20 cluster. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

A previous work by the authors has shown that the usual spin Hamiltonian used to model the magnetic spectra of mixed valence compounds was not sufficient to reproduce the magnetic spectrum of the molecule [Fe2(OH)3(NH3)6]2+. In the present paper, the spin Hamiltonian is confronted to correlated ab initio calculations. The discrepancy between this Hamiltonian and the calculations is investigated and explained. It is pointed out that the multiconfigurational nature of the transition metal is responsible for this discrepancy. However, we show that this effect can easily be treated at the complete active space self-consistent field (CASSCF) level and that no further correlation treatment is needed. The spin Hamiltonian, which reproduces very well the minimal CASSCF results, could not be improved to recover the multireference effects. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

In this paper we propose and discuss the laser-induced circular dichroism (LICD) effect, which is expected to occur in linear molecules pumped by a strong circular resonant light beam. The effect is to be detected via the absorption of a weak circularly polarized probe beam on another transition. Analogous to the external magnetic field in magnetic circular dichroism the resonant circular polarized pumping optical field can induce the nonzero antisymmetric rotational polarizabilities of a linear molecule, and cause the LICD effect. LICD contains three distinct contributions from M-dependent splittings of the sublevels |JM> due to the ac Stark effect, from the differences of Boltzmann statistical distributions among the ground state sublevels |JM> due to the ac Stark splittings, and from the changes of occupation probability in rotational sublevels |JM> due to the pumping effect. The fundamental formulas for the above three terms of LICD have been deduced by the density matrix method. As an example, the LICD for CO molecules have been calculated. The results indicate that in comparison with the rotationally resolved magnetic vibrational circular dichroism experiment, LICD may be measurable and form a basis of a different kind of CD spectroscopy. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The aim of this paper is to elucidate the role played by the bosonic/fermionic character of N He atoms solvating a Br2(X) molecule. To this end, an adiabatic model in the molecular stretching coordinate is assumed and the ground energy levels of the complexes are searched by means of Hartree (or Hartree-Fock) Quantum Chemistry calculations for 4He (or 3He) solvent atoms. Simulations of vib-rotational Raman spectra point at the spin multiplicity as the main feature responsible for the drastic difference in the rotational structures of molecules embedded in boson or fermion helium drops as already observed by the experiments of Grebenev et al. [S. Grebenev, J. P. Toennies, and A. F. Vilesov, Science 279 (1998) 2083]. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The Sm+O chemiionization reaction has been investigated theoretically using a method that allows for correlation and relativistic effects. Potential energy curves have been calculated for several electronic states of SmO and SmO+. Comparison with available spectroscopic and thermodynamic values for these species is reported and a mechanism for the chemiionization reaction Sm+O is proposed. The importance of spin–orbit coupling in the excited states of SmO, in allowing this chemiionization reaction to take place, has been revealed by these calculations. This paper shows the metal-plus-oxidant chemiionization reaction. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Phase space representations of quantum mechanics constitute useful tools to study vibrations in molecular systems. Among all possibilities, the Husimi function or coherent state representation is very widely used, its maxima indicating which regions of phase space are relevant in the dynamics of the system. The corresponding zeros are also a good indicator to investigate the characteristics of the eigenstates, and it has been shown how the corresponding distributions can discriminate between regular, irregular, and scarred wave functions. In this paper, we discuss how this result can be understood in terms of the overlap between coherent states and system eigenfunctions. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

This paper presents an exact solution for the free energy of linear solvation of a dipolar solute in an arbitrary dielectric material with a microscopic spectrum of polarization fluctuations. The solution is given in terms of wave vector-dependent longitudinal and transverse structure factors of the polarization fluctuations in the pure dielectric. Good agreement with computer simulations of dipole solvation in dipolar and dipolar–quadrupolar liquids is achieved. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The conformational isomerization dynamics of N-acetyl tryptophan methyl amide (NATMA) and N-acetyl tryptophan amide (NATA) have been studied using the methods of IR-UV hole-filling spectroscopy (HFS) and IR-induced population transfer spectroscopy (IR-PTS), which were developed for this purpose. Single conformations of these molecules were selectively excited in well-defined NH stretch fundamentals. This excess energy was used to drive conformational isomerization. By carrying out the infrared excitation early in a supersonic expansion, the excited molecules were recooled into their zero-point levels, partially refilling the hole created in the ground state population of one of the conformers, and creating gains in population in other conformers. These changes in population were detected using laser-induced fluorescence downstream in the expansion. In HFS, the IR wavelength is fixed and the UV laser tuned in order to determine where the population went following selective infrared excitation. In IR-PTS, the UV is fixed to monitor the population of a given conformation, and the IR is tuned to record the IR-induced changes in the population of the monitored conformer. Besides demonstrating the capability of the experiment to change the downstream conformational population distribution, the IR-PTS scans were used to extract two quantitative results: (i) The fractional populations of the conformers in the absence of the infrared, and (ii) the isomerization quantum yields for each of the six unique amide NH stretch fundamentals (three conformers each with two amide groups). The method for obtaining quantum yields is described in detail. In both NATMA and NATA, the quantum yields show modest conformational specificity, but only a hint of vibrational mode specificity. The prospects for the hole-filling technique for providing insight into energy flow in large molecules are discussed, leaving a more detailed theoretical modeling to the adjoining paper [Evans et al. J. Chem. Phys. 120, 148 (2004)]. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Multicomponent emission bands are recorded for the [sup 3]P[sub 1]→[sup 1]S[sub 0] transition of atomic mercury isolated at single sites in solid Ar, Kr, and Xe matrices. A blueshift observed at elevated temperatures on the 273 nm emission of Hg/Xe is identified in line shape analysis as arising from decreasing intensity of the central component in the band profile. The origin of the multiple components in the emission bands is ascribed to the existence of several vibronic modes which lead to excited state stabilization in the Hg([sup 3]P[sub 1])/RG matrix systems. A detailed description of these modes and their energetics is presented in the paper directly following. Photoexcitation of the [sup 3]P[sub 1] state also yields small amounts of [sup 3]P[sub 0] state emission. Hg atom [sup 3]P[sub 1] to [sup 3]P[sub 0] state intramultiplet relaxation (IMR) is most efficient in Hg/Xe where the ratio of this relaxation channel to [sup 3]P[sub 1] state radiative decay is 1/200 as established in time-integrated emission spectra. Despite the weakness of IMR, pulsed laser excitation combined with photon counting detection provide time-gated [sup 3]P[sub 0] state emission spectra largely free of the more intense [sup 3]P[sub 1] state emission. Such emission spectra recorded under high resolution for the [sup 3]P[sub 0]→[sup 1]S[sub 0] transition of atomic mercury isolated in solid Xe provide the first example of the occurrence of a zero-phonon lines for a metal atom isolated in a rare gas matrix. Wp line shape analysis conducted on the emission bands recorded at specific temperatures, confirm this assignment. The electron–phonon coupling strength (Huang-Rhys, S factor) extracted in the line shape fits for the Hg/Xe transition is 1.3. Slightly stronger coupling is identified in Kr (S=2.2) and stronger still in Ar (S=3.3). Analysis of the diatomic Hg·RG potential energy curves reveal that the origin of the weak electron–phonon coupling lies primarily in the similarity in the ground and excited states, but also indicates the site size offered by the host solid plays a role. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The wealth of information carried by the two-dimensional Raman spectra of liquids comes with a price. The signal arises from a mixture of two entirely different mechanisms, each of which reveals its own perspective on intermolecular dynamics. In this paper we analyze the dynamical origins and consequences of both of these mechanisms. By applying an instantaneous-normal-mode formalism to the two-dimensional Raman spectrum of a solution of CS[sub 2] dissolved in Xe, we find discernable differences in the specific molecular degrees of freedom and basic symmetries that contribute to each mechanism. We then show how these differences can be exploited to separate these mechanisms experimentally. In particular, we point out how it should be possible to use two-dimensional Raman spectroscopy to measure the explicitly anharmonic contributions to liquid dynamics without obscuring the results by simultaneously measuring the nonlinear coupling of the polarizability to that dynamics. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The photodissociation of allyl-d[sub 2] iodide (H[sub 2]C=CDCH[sub 2]I) and the dynamics of the nascent allyl-d[sub 2] radical (H[sub 2]CCDCH[sub 2]) were studied using photofragment translational spectroscopy. A previous study found the allyl radical stable at internal energies up to 15 kcal/mol higher than the 60 kcal/mol barrier to allene+H formation as the result of a centrifugal barrier. The deuterated allyl radical should then also show a stability to secondary dissociation at internal energies well above the barrier due to centrifugal effects. A comparison in this paper shows the allyl-d[sub 2] radical is stable to allene+D formation at energies of 2–3 kcal/mol higher than that of the nondeuterated allyl radical following photolysis of allyl iodide at 193 nm. This is most likely a result of a combination of the slight raising of the barrier from the difference in zero-point levels and a reduction of the impact parameter of the dissociative fragments due to the decrease in frequency of the C–D bending modes, and therefore allene+D product orbital angular momentum, |Lvector |=μ|vvector [sub rel]|b. The integrated signal taken at m/e=40 (allene) and m/e=41 (allene-d[sub 1] and propyne-d[sub 3]) shows a minor fraction of the allyl-d[sub 2] radicals isomerize to the 2-propenyl radical, in qualitative support of earlier conclusions of the domination of direct allene+H formation over isomerization. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]