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Machine-learned representations of potential energy surfaces generated in the output layer of a feedforward neural network are becoming increasingly popular. One difficulty with neural-network output is that it is often unreliable in regions where training data is missing or sparse. Human-designed potentials often build in proper extrapolation behavior by choice of functional form. Because machine learning is very efficient, it is desirable to learn how to add human intelligence to machine-learned potentials in a convenient way. One example is the well understood feature of interaction potentials that they vanish when subsystems are too far separated to interact. In this article, we present a way to add a new kind of activation function to a neural network to enforce low-dimensional constraints. In particular the activation function depends parametrically on all the input variables. We illustrate the use of this step by showing how it can force an interaction potential to go to zero at large subsystem separations with either inputting a specific functional form for the potential or adding data to the training set in the asymptotic region of geometries where the subsystems are separated. In the process of illustrating this, we present an improved set of potential energy surfaces for the 14 lowest 3A´ states of O3. The method is more general than this example, and it may be used to add other low-dimensional knowledge or lower-level knowledge to machine-learned potentials. In addition to the O3 example, we present a greater-generality method called parametrically managed diabatization by deep neural network (PM-DDNN) that is an improvement on our previously presented permutationally restrained diabatization by deep neural network (PR-DDNN).

Machine-learned representations of potential energy surfaces generated in the output layer of a feedforward neural network are becoming increasingly popular. One difficulty with neural-network output is that it is often unreliable in regions where training data is missing or sparse. Human-designed potentials often build in proper extrapolation behavior by choice of functional form. Because machine learning is very efficient, it is desirable to learn how to add human intelligence to machine-learned potentials in a convenient way. One example is the well understood feature of interaction potentials that they vanish when subsystems are too far separated to interact. In this article, we present a way to add a post-activation step to a neural network to enforce low-dimensional constraints. We illustrate the use of this step by showing how it can force an interaction potential to go to zero at large subsystem separations with either inputting a specific functional form for the potential or adding data to the training set in the asymptotic region of geometries where the subsystems are separated. In the process of illustrating this, we present an improved set of potential energy surfaces for the 14 lowest 3A´ states of O3. The method is more general than this example, and it may be used to add other low-dimensional knowledge to machine-learned potentials. As an example, we present a greater-generality method called physically managed diabatization by deep neural network (PM-DDNN) that is an improvement on our previously presented permutationally restrained diabatization by deep neural network (PR-DDNN).

Direct dynamics by mixed quantum–classical nonadiabatic methods is an important tool for understanding processes involving multiple electronic states. Very often, the computational bottleneck of such direct simulation comes from electronic structure theory. For example, at every time step of a trajectory, nonadiabatic dynamics requires potential energy surfaces, their gradients, and the matrix elements coupling the surfaces. The need for the couplings can be alleviated by employing the time derivatives of the wave functions, which can be evaluated from overlaps of electronic wave functions at successive timesteps. However, evaluation of overlap integrals is still expensive for large systems. In addition, for electronic structure methods for which the wave functions or the coupling matrix elements are not available, nonadiabatic dynamics algorithms become inapplicable. In this work, building on recent work by Baeck and An, we propose new nonadiabatic dynamics algorithms that only require adiabatic potential energies and their gradients. The new methods are named curvature- driven coherent switching with decay of mixing (κCSDM) and curvature-driven trajectory surface hopping (κTSH). We show how powerful these new methods are in terms of computer time and good agreement with methods employing nonadiabatic coupling vectors computed in conventional ways. The lowering of the computational cost will allow longer nonadiabatic trajectories and greater ensemble averaging to be affordable, and the ability to calculate the dynamics without electronic structure coupling matrix elements extends the dynamics capability to new classes of electronic structure methods.

Decoherence is the tendency of a time-evolved reduced density matrix for a subsystem to assume a form corresponding to a statistical ensemble of states rather than a coherent combination of pure-state wave functions. When a molecular process involves changes in the electronic state and the coordinates of the nuclei, as in ultraviolet or visible light photochemistry or electronically inelastic collisions, the reduced density matrix of the electronic subsystem suffers decoherence, due to its interaction with the nuclear subsystem. We present the background necessary to conceptualize this decoherence; in particular, we discuss the density matrix description of pure states and mixed states, and we discuss pointer states and decoherence time. We then discuss how decoherence is treated in the coherent switching with decay of mixing algorithm and the trajectory surface hopping method for semiclassical calculations of electronically nonadiabatic processes.

The photoinduced ring-opening reaction of 1,3-cyclohexadiene to produce 1,3,5-hexatriene is a classic electrocyclic reaction and is also a prototype for many reactions of biological and synthetic importance. Here, we simulate the ultrafast nonadiabatic dynamics of the reaction in the manifold of the three lowest valence electronic states by using extended multistate complete-active-space second-order perturbation theory (XMS-CASPT2) combined with the curvature-driven coherent switching with decay of mixing (κCSDM) dynamical method. We obtain an excited-state lifetime of 79 fs, and a product quantum yield of 40% from the 500 trajectories initiated in the S

Simulations of electronically nonadiabatic processes may employ either the adiabatic or diabatic representation. Direct dynamics calculations are usually carried out in the adiabatic basis because the energy, force, and state coupling can be evaluated directly by many electronic structure methods. However, although its straightforwardness is appealing, direct dynamics is expensive when combined with quantitatively accurate electronic structure theories. This generates interest in analytically fitted surfaces to cut the expense, but the cuspidal ridges of the potentials and the singularities and vector nature of the couplings at high-dimensional, nonsymmetry-determined intersections in the adiabatic representation make accurate fitting almost impossible. This motivates using diabatic representations, where the surfaces are smooth and the couplings are also smooth and-importantly-scalar. In a recent previous work, we have developed a method called diabatization by deep neural network (DDNN) that takes advantage of the smoothness and nonuniqueness of diabatic bases to obtain them by machine learning. The diabatic potential energy matrices (DPEMs) learned by the DDNN method yield not only diabatic potential energy surfaces (PESs) and couplings in an analytic form useful for dynamics calculations, but also adiabatic surfaces and couplings in the adiabatic representation can be calculated inexpensively from the transformation. In the present work, we show how to extend the DDNN method to produce good approximations to global permutationally invariant adiabatic PESs simultaneously with DPEMs. The extended method is called permutationally restrained DDNN.

Electronically nonadiabatic dynamics methods based on a self-consistent potential, such as semiclassical Ehrenfest and coherent switching with decay of mixing, have a number of advantages but are computationally slower than approximations based on an unaveraged potential because they require evaluation of all components of the nonadiabatic coupling vector. Here we introduce a new approximation to the self-consistent potential that does not have this computational drawback. The new approximation uses time-derivative couplings evaluated by overlap integrals of electronic wave functions to approximate the nonadiabatic coupling terms in the equations of motion. We present a numerical test of the method for ethylene that shows there is little loss of accuracy in the ensemble-averaged results. This new approximation to the self-consistent potential makes direct dynamics calculations with self-consistent potentials more efficient for complex systems and makes them practically affordable for some cases where the cost was previously too high.

The relationships between Kohn-Sham (KS) and generalized KS (GKS) density functional orbital energies and fundamental gaps or optical gaps raise many interesting questions including the physical meanings of KS and GKS orbital energies when computed with currently available approximate density functionals (ADFs). In this work, by examining three diverse databases with various ADFs, we examine such relations from the point of view of the exciton shift of quasiparticle theory. We start by calculating a large number of excitation energies by time-dependent density functional theory (TDDFT) with a large number of ADFs. To relate the exciton shift implicit in TDDFT to the exciton shift that is explicit in Green's function theory, we define the exciton shift in TDDFT as the difference of the response shift and the quasiparticle shift. We found a strong correlation between the response shift and the amount of Hartree-Fock exchange included in the density functional, with the response shift varying between -1 and 5 eV. This range is an order of magnitude larger than the mean errors of the TDDFT excitation energies. This result suggests that, with currently available functionals, the KS or GKS orbital energies should be treated as intermediate mathematical variables in the calculation of excitation energies rather than as the energies of independent-particle reference states for quasiparticle theory.

Direct nonadiabatic dynamics is used to study processes involving multiple electronic states from small molecules to materials. Compared with dynamics with fitted analytical potential energy surfaces, direct dynamics is more user-friendly in that it obtains all needed energies, gradients, and nonadiabatic couplings (NACs) by electronic structure calculations. However, the NAC that is usually used does not conserve angular momentum or the center of mass in widely used mixed quantum-classical nonadiabatic dynamics algorithms, in particular, trajectory surface hopping, semiclassical Ehrenfest, and coherent switching with decay of mixing. We show that by using a projection operator to remove the translational and rotational components of the originally computed NAC, one can restore the conservation.

Quantitative simulations of electronically nonadiabatic molecular processes require both accurate dynamics algorithms and accurate electronic structure information. Direct semiclassical nonadiabatic dynamics is expensive due to the high cost of electronic structure calculations, and hence it is limited to small systems, limited ensemble averaging, ultrafast processes, and/or electronic structure methods that are only semiquantitatively accurate. The cost of dynamics calculations can be made manageable if analytic fits are made to the electronic structure data, and such fits are most conveniently carried out in a diabatic representation because the surfaces are smooth and the couplings between states are smooth scalar functions. Diabatic representations, unlike the adiabatic ones produced by most electronic structure methods, are not unique, and finding suitable diabatic representations often involves time-consuming nonsystematic diabatization steps. The biggest drawback of using diabatic bases is that it can require large amounts of effort to perform a globally consistent diabatization, and one of our goals has been to develop methods to do this efficiently and automatically. In this Feature Article, we introduce the mathematical framework of diabatic representations, and we discuss diabatization methods, including adiabatic-to-diabatic transformations and recent progress toward the goal of automatization.

Dissociation and energy transfer in high-energy collisions of O2 play important roles in simulating thermal energy content and heat flux in flows around hypersonic vehicles. Furthermore, atomic oxygen reactions on the vehicle surface are an important contributor to heat shield erosion. Molecular dynamics modeling is needed to better understand the relevant rate processes. Because it is necessary to model the gas flows in high-temperature shock waves, electronically excited states of O2 and O can be populated, and molecular dynamics simulations should include collisions of electronically excited species and electronically nonadiabatic collisions. This requires potential energy surfaces and state couplings for many energetically accessible electronic states. Here we report a systematic strategy to calculate such surfaces and couplings. We have applied this method to the fourteen lowest-energy potential energy surfaces in the 3 A′ manifold of O3, and we report a neural-network fit to diabatic potential energy matrix (DPEM). We illustrate the use of the resulting DPEM by carrying out semiclassical dynamics calculations of cross sections for excitation of O2 in 3 A′ collisions with O at two collision energies; these dynamics calculations are carried out by the curvature-driven coherent switching with decay of mixing method.

The utility of optoelectronic materials can be greatly reduced by the presence of efficient pathways for nonradiative recombination (NRR). Lead halide perovskites have garnered much attention in recent years as materials for solar energy conversion, because they readily absorb visible light, are easy to synthesize, and have a low propensity for NRR. Here we report a theoretical study of the pathways for NRR in an archetypal lead halide perovskite: CsPbBr3. Specifically, we identified a set of conical intersection (CIs) in both a molecule-sized cluster model (Cs4PbBr6) and nanoparticle model (Cs12Pb4Br20) of the CsPbBr3 surface. The energies of the minimal energy CIs, corrected for both dynamical electron correlation and spin-orbit coupling, are well above the bulk band gap of CsPbBr3, suggesting that these intersections do not provide efficient pathways for NRR in this material. Analysis of the electronic structure at these intersections suggests that the ionic nature of the bonds in CsPbBr3 may play a role in the high energy of these CIs. The lowest-energy intersections all involve charge transfer over long distances, whether it be across a dissociated bond or between neighboring unit cells.

The complete active space self-consistent field (CASSCF) method has seen broad adoption due to its ability to describe the electronic structure of both the ground and excited states of molecules over a broader swath of the potential energy surface than is possible with the simpler Hartree–Fock approximation. However, it also has a reputation for being unwieldy, computationally costly, and un-black-box. Here, we discuss a class of alternatives, complete active space configuration interaction (CASCI) methods, paying particular attention to their application to electronic excited states. The goal of this Perspective is fourfold. First, we argue that CASCI is not merely an approximation to CASSCF, in that it can be designed to have important qualitative advantages over CASSCF. Second, we present several insights drawn from our experience experimenting with different schemes for computing orbitals to be employed in CASCI. Third, we argue that CASCI is well suited for application to nanomaterials. Finally, we reason that, with the rise in new low-scaling approaches for describing multireference systems, there is a greater need than ever to develop new methods for defining orbitals that provide an efficient and accurate description of both static correlation and electronic excitations in a limited active space.

We evaluate the effect of electronic decoherence on intersystem crossing in the photodynamics of thioformaldehyde. First, we show that the state-averaged complete-active-space self-consistent field electronic structure calculations with a properly chosen active space of 12 active electrons in 10 active orbitals can predict the potential energy surfaces and the singlet–triplet spin–orbit couplings quite well for CH2S, and we use this method for direct dynamics by coherent switching with decay of mixing (CSDM). We obtain similar dynamical results with CSDM or by adding energy-based decoherence to trajectory surface hopping, with the population of triplet states tending to a small steady-state value over 500 fs. Without decoherence, the state populations calculated by the conventional trajectory surface hopping method or the semiclassical Ehrenfest method gradually increase. This difference shows that decoherence changes the nature of the results not just quantitatively but qualitatively.

Understanding nonadiabatic dynamics is important for chemical and physical processes involving multiple electronic states. Direct nonadiabatic dynamics simulations are often employed to observe such processes on a femtosecond time scale. One often needs to do the simulation on a longer time scale, but direct simulation based on electronic structure calculations of the surfaces and couplings is expensive due to the large number of electronic structure calculations needed for ensemble averaging or simulation of longer-time processes. An alternative approach is to construct an analytical representation of potential energy surfaces (PESs) and couplings, which allows for faster dynamics calculations. Diabatic representations are preferred for such purposes because of the smoothness of the surfaces and couplings and the scalar nature of the couplings. However, many diabatization procedures are complicated by the need to consider orbitals or vector coupling elements, and these can make the process very labor-intensive. To circumvent these difficulties, we here propose diabatization by a deep neural network (DDNN) based on a new architecture for a deep neural network that requires neither orbital input nor vector input. The DDNN method allows convenient and semiautomatic diabatization, and it is demonstrated here for a model problem and for producing diabatic potential energy matrices for thiophenol.

Simulation of electronically nonadiabatic dynamics is an important tool for understanding the mechanisms of photochemical and photophysical processes. Two contrasting methods in which the electrons are treated quantum mechanically while the nuclei are treated classically are semiclassical Ehrenfest dynamics and trajectory surface hopping; neither method in its original form includes decoherence. Decoherence in the context of electronically nonadiabatic dynamics refers to the gradual collapse of a coherent quantum mechanical electronic state under the scrutiny of nuclear motion into a mixture of stable pointer states. This is modeled in the coherent switches with decay of mixing (CSDM) method by the decay of the off-diagonal elements of the electronic density matrix. Here, we present an implementation of CSDM in the SHARC program; a key element of the new implementation is the use of a different propagator than that used previously in the ANT program.

Electronically nonadiabatic photodissociation can be investigated in detail by experiments. This provides an opportunity to validate the current theory of electronically nonadiabatic processes, but is great challenge because the time scale of photodissociation processes can be long compared to the current capability for accurate direct dynamics simulations. To circumvent this difficulty, we have been using analytic diabatic potential energy matrices, such that the simulation time scale can be extended to the nanosecond region without neglecting the effects of external electron correlation. In previous work, we have developed full-dimensional three-state potential energy matrices for thioanisole photodissociation. In the current work, we extend this work in two main ways: (i) we improve the treatment of the initial torsional potential, and (ii) we shift the potential energy surfaces to investigate the quantitative effect on the dissociation lifetimes and product branching ratios of changing the energy and location of the S1–S2 conical intersection.

It is well known that classical trajectories, even if they are initiated with zero point energy (ZPE) in each mode (trajectories initiated this way are commonly called quasiclassical trajectories), do not maintain ZPE in the final states. The energy of high-frequency modes will typically leak into low-frequency modes or relative translation of subsystems during the time evolution. This can lead to severe problems such as unphysical dissociation of a molecule, production of energetically disallowed reaction products, and unphysical product energy distributions. Here a new molecular dynamics method called extended Hamiltonian molecular dynamics (EHMD) is developed to improve the ZPE problem in classical molecular dynamics. In EHMD, two images of a trajectory are connected by one or more springs. The EHMD method is tested with the Henon-Heiles Hamiltonian in reduced and real units and with a Hamiltonian with quartic anharmonicity in real units, and the method is found to improve zero-point maintenance as intended.

Conical intersections are well known to introduce nonradiative decay pathways in molecules, but have only recently been implicated in nonradiative recombination processes in materials. Here we apply excited state ab initio molecular dynamics simulations based on a multireference description of the electronic structure to defective silicon nanocrystals up to 1.7 nm in diameter to search for accessible nonradiative recombination pathways. Dangling bond defects are found to induce conical intersections between the ground and first excited electronic states of five systems of various sizes. These defect-induced conical intersections are accessible at energies that are in the visible range (2.4–2.7 eV) and very weakly dependent on particle size. The dynamic simulations suggest that these intersections are accessed 40–60 fs after creation of a defect-localized excitation. This ultrafast recombination is attributed to the fact that Jahn–Teller distortion on the first excited state drives the defect directly towards a conical intersection with the ground electronic state.

Butadiene is the simplest polyene and has long served as a model system for many chemical and spectroscopic properties. However, this small molecule has presented significant challenges to theoretical chemistry. The 21Ag state, which is dark but photochemically important, is a prime source of this difficulty. Previous studies attributed the notorious difficulty in treating this state to strong double excitation character of the 21Ag state, which prevents the application of linear response (LR) methods. Therefore, one would require methods with much higher computational cost, especially for the analogues of this state in longer polyenes, and consequently studies of longer polyenes are very limited. In the present work, we argue that the difficulty stems more significantly from the inherently multiconfigurational character of the ground state. In addition, we validate the possibility of employing LR time-dependent density functional theory to investigate such a state with reasonable accuracy.

Defects are known to introduce pathways for the nonradiative recombination of electronic excitations in semiconductors, but implicating a specific defect as a nonradiative center remains challenging for both experiment and theory. In this Perspective, we present recent progress toward this goal involving the identification and characterization of defect-induced conical intersections (DICIs), points of degeneracy between the ground and first excited electronic states of semiconductor materials that arise from the deformation of specific defects. Analysis of DICIs does not require the assumption of weak correlation between the electron and hole nor of stationary nuclei. It is demonstrated that in some cases an energetically accessible DICI is present even when no midgap state is predicted by single-particle theories (e.g., density functional theory). We review recent theoretical and computational developments that enable the location of DICIs in semiconductor nanomaterials and present insights into the photoluminescence of silicon nanocrystals gleaned from DICIs.

Time-dependent Kohn–Sham density functional theory has been used successfully to compute vertical excitation energies, especially for large molecular systems. However, the lack of double excitation character in the excited amplitudes produced by linear response in the adiabatic approximation holds it back from broader applications in photochemistry; for example, it shows (3N – 7)-dimensional conical intersection seams (where N is the number of atoms) between ground and excited states, although the correct dimensionality is 3N – 8. In this letter, we present a new, conceptually simple, easy-to-implement, and easy-to-use way to employ time-dependent Kohn–Sham density functional theory that has global accuracy comparable with the conventional single-functional version and that recovers the double cone topology of the potential energy surfaces at S1/S0 conical intersection seams. The new method is called the dual-functional Tamm–Dancoff approximation (DF-TDA).

We have employed extended multiconfiguration quasidegenerate perturbation theory, fourfold-way diabatic molecular orbitals, and configurational uniformity to develop a global three-state diabatic representation of the potential energy surfaces and their couplings for the electronically nonadiabatic reaction OH

The ability to predict and describe nonradiative processes in molecules via the identification and characterization of conical intersections is one of the greatest recent successes of theoretical chemistry. Only recently, however, has this concept been extended to materials science, where nonradiative recombination limits the efficiencies of materials for various optoelectronic applications. In this review, we present recent advances in the theoretical study of conical intersections in semiconductor nanomaterials. After briefly introducing conical intersections, we argue that specific defects in materials can induce conical intersections between the ground and first excited electronic states, thus introducing pathways for nonradiative recombination. We present recent developments in theoretical methods, computational tools, and chemical intuition for the prediction of such defect-induced conical intersections. Through examples in various nanomaterials, we illustrate the significance of conical intersections for nanoscience. We also discuss challenges facing research in this area and opportunities for progress.

The photophysical properties of emissive silicon nanomaterials depend strongly on the chemical composition and structure of their surfaces, and the development of a causal, microscopic understanding of this relationship is highly desirable. One surface-dependent property of interest is the propensity for nonradiative recombination (NRR). In this work, we apply ab initio theoretical methods to investigate the mechanism of NRR in a silicon nanocrystal with a single surface silanol group. Ab initio multiple spawning simulations of an electronically excited cluster model (Si7H11OH) indicate ultrafast nonradiative decay to the electronic ground state. A multireference electronic structure study demonstrates that this nonradiative decay occurs near conical intersections between the ground and first excited electronic states of the cluster. These intersections are accessed after stretching of the bond between the silanol silicon atom and an adjacent silicon atom. The presence of this intersection in a true nanom...

Recently we have developed the dual-functional Tamm–Dancoff approximation (DF-TDA) method. DF-TDA is an alternative to linear-response time-dependent density functional theory (LR-TDDFT) with the advantage of providing a correct double-cone topology of S1/S0 conical intersections. In the DF-TDA method, we employ different functionals, which are denoted G and F, for orbital optimization and Hamiltonian construction. We use the notation DF-TDA/G:F. In the current work, we propose that G be the same as F except for having 100% Hartree–Fock exchange. We use the notation F100 to denote functional F with this modification. A motivation for this is that functionals with 100% Hartree–Fock exchange are one-electron self-interaction-free. Here we validate the use of F100/M06 to compute vertical excitation energies and the global potential energy surface of ammonia near a conical intersection to further validate the F100 method for photochemical problems.

We report a combined experimental and theoretical study of the relationship between the surface structure of silicon nanocrystals synthesized in a nonthermal plasma reactor and their photoluminescence (PL) yields. Upon heating to 160 °C, a significant change in the SiH stretch region of the vibrational spectrum is observed indicating a decrease in surface SiH3 groups, which correlates with an increase in the PL yield. Effusion of SiHx and Si2H2x from the material is detected by residual gas analysis upon heating to temperatures below 200 °C, suggesting a weakly bound species. Analysis of electron paramagnetic resonance spectra before and after heating points to a small reduction in the density of dangling bonds upon heating but this reduction does not correlate with the increase in PL yield. Electronic structure calculations indicate that SiH3– groups may hypervalently bond to fully coordinated surface silicon atoms, resulting in a relatively weak (0.70 eV) bond that is consistent with the experimentally ...

Nonradiative recombination of excitations in semiconductors limits the performance of photovoltaics, light-emitting diodes, photocatalysts, and other devices. Herein we investigate the role that two known defects on the oxidized surface of silicon play in nonradiative recombination in silicon nanocrystals. We apply ab initio multiple spawning and multireference electronic structure methods to model the nonradiative processes which follow excitation of two cluster models of silicon epoxide defects that differ in the oxidation state of their respective silicon atoms. We find conical intersections in both clusters, and these intersections are found to be accessible at energies corresponding to visible wavelengths. In both cases, photochemical opening of the epoxide ring precedes nonradiative decay. These results support the hypothesis that conical intersections associated with specific defect structures on the oxidized surface of silicon nanocrystals facilitate nonradiative recombination. Discussion regardin...

A new complete active space configuration interaction (CASCI) method was recently introduced that uses state-averaged natural orbitals from the configuration interaction singles method (configuration interaction singles natural orbital CASCI, CISNO-CASCI). This method has been shown to perform as well or better than state-averaged complete active space self-consistent field for a variety of systems. However, further development and testing of this method have been limited by the lack of available analytic first derivatives of the CISNO-CASCI energy as well as the derivative coupling between electronic states. In the present work, we present a Lagrangian-based formulation of these derivatives as well as a highly efficient implementation of the resulting equations accelerated with graphical processing units. We demonstrate that the CISNO-CASCI method is practical for dynamical simulations of photochemical processes in molecular systems containing hundreds of atoms.

Time-dependent Kohn-Sham density functional theory has been used successfully to compute vertical excitation energies, especially for large molecular systems. However, the lack of double excitation character in the excited amplitudes produced by linear response in the adiabatic approximation holds it back from broader applications in photochemistry; for example, it shows (3N - 7)-dimensional conical intersection seams (where N is the number of atoms) between ground and excited states, although the correct dimensionality is 3N - 8. In this letter, we present a new, conceptually simple, easy-to-implement, and easy-to-use way to employ time-dependent Kohn-Sham density functional theory that has global accuracy comparable with the conventional single-functional version and that recovers the double cone topology of the potential energy surfaces at S

Oxidation of the surface of well-passivated silicon nanocrystals introduces defects which dramatically affect the optical properties of the material. One such defect is the silicon–oxygen double bond, which has been implicated as the source of the unusual particle-size-independent S-band photoluminescence of oxidized silicon nanocrystals. Herein, we investigate the photodynamics of this defect by application of a first-principles nonadiabatic molecular dynamics approach to a cluster model containing a silicon–oxygen double bond. Upon excitation, pyramidalization occurs about the double-bonded silicon atom, leading to a conical intersection between the ground and first excited state. This conical intersection facilitates nonradiative decay, resulting in the internal conversion of 7% of the excited population in the first picosecond after excitation. Extrapolation to longer times suggests that nonradiative decay via conical intersection proceeds faster than the microsecond photoluminescence lifetime of sili...

We have employed extended multiconfiguration quasidegenerate perturbation theory, fourfold-way diabatic molecular orbitals, and configurational uniformity to develop a global three-state diabatic representation of the potential energy surfaces and their couplings for the electronically nonadiabatic reaction OH* + H2 → H2O + H, where * denotes electronic excitation to the A 2Σ+ state. To achieve sign consistency of the computed diabatic couplings, we developed a graphics processing unit-accelerated algorithm called the cluster-growing algorithm. Having obtained consistent signs of the diabatic couplings, we fit the diabatic matrix elements (which consist of the diabatic potentials and the diabatic couplings) to analytic representations. Adiabatic potential energy surfaces are generated by diagonalizing the 3 × 3 diabatic potential energy matrix. The comparisons between the fitted and computed diabatic matrix elements and between the originally computed adiabatic potential energy surfaces and those generated from the fits indicate that the current fit is accurate enough for dynamical studies, and it may be used for quantal or semiclassical dynamics calculations.

We apply multireference electronic structure calculations to demonstrate the presence of conical intersections between the ground and the first excited electronic states of three silicon nanocrystals containing defects characteristic of the oxidized silicon surface. These intersections are accessible upon excitation at visible wavelengths and are predicted to facilitate nonradiative recombination with a rate that increases with decreasing particle size. This work illustrates a new framework for identifying defects responsible for nonradiative recombination.

Interaction of intense laser pulses with atoms and molecules is at the forefront of atomic, molecular, and optical physics. It is the gateway to powerful new tools that include above threshold ionization, high harmonic generation, electron diffraction, molecular tomography, and attosecond pulse generation. Intense laser pulses are ideal for probing and manipulating chemical bonding. Though the behavior of atoms in strong fields has been well studied, molecules under intense fields are not as well understood and current models have failed in certain important aspects. Molecules, as opposed to atoms, present confounding possibilities of nuclear and electronic motion upon excitation. The dynamics and fragmentation patterns in response to the laser field are structure sensitive; therefore, a molecule cannot simply be treated as a "bag of atoms" during field induced ionization. In this article we present a set of experiments and theoretical calculations exploring the behavior of a large collection of aryl alkyl ketones when irradiated with intense femtosecond pulses. Specifically, we consider to what extent molecules retain their molecular identity and properties under strong laser fields. Using time-of-flight mass spectrometry in conjunction with pump-probe techniques we study the dynamical behavior of these molecules, monitoring ion yield modulation caused by intramolecular motions post ionization. The set of molecules studied is further divided into smaller sets, sorted by type and position of functional groups. The pump-probe time-delay scans show that among positional isomers the variations in relative energies, which amount to only a few hundred millielectronvolts, influence the dynamical behavior of the molecules despite their having experienced such high fields (V/Å). High level ab initio quantum chemical calculations were performed to predict molecular dynamics along with single and multiphoton resonances in the neutral and ionic states. We propose the following model of strong-field ionization and subsequent fragmentation for polyatomic molecules: Single electron ionization occurs on a suboptical cycle time scale, and the electron carries away essentially all of the energy, leaving behind little internal energy in the cation. Subsequent fragmentation of the cation takes place as a result of further photon absorption modulated by one- and two-photon resonances, which provide sufficient energy to overcome the dissociation energy. The proposed hypothesis implies the loss of a photoelectron at a rate that is faster than intramolecular vibrational relaxation and is consistent with the observation of nonergodic photofragmentation of polyatomic molecules as well as experimental results from many other research groups on different molecules and with different pulse durations and wavelengths.

Localization of electronic excitations at molecule-sized semiconductor defects often precedes non-radiative (NR) decay, and it is known that many molecules undergo NR decay via conical intersection. Herein, we report the direct simulation of fast and efficient NR decay via a conical intersection at a known semiconductor defect. It is suggested that this silicon epoxide defect may selectively quench photoluminescence (PL) in small silicon nanocrystals (band gap > ∼2.8 eV), and thus influence both the observed PL yield and PL energy of oxidized silicon nanocrystals.

We report order-of-magnitude quantum coherent control of the yield of photofragment ions following the creation of electronic coherence in the Rydberg states of dicyclopentadiene (C10H12) molecules using a pair of phase-locked femtosecond near-infrared laser pulses.

Organic light emitting diodes based on fluorophores with a propensity for thermally activated delayed fluorescence (TADF) are able to circumvent limitations imposed on device efficiency by spin statistics. Molecules with a propensity for TADF necessarily have two properties: a small gap between the lowest lying singlet and triplet excited states and a large transition dipole moment for fluorescence. In this work, we demonstrate the use of a genetic algorithm to search a region of chemical space for molecules with these properties. This algorithm is based on a flexible and intuitive representation of the molecule as a tree data structure, in which the nodes correspond to molecular fragments. Our implementation takes advantage of hybrid parallel graphics processing unit accelerated computer clusters to allow efficient sampling while retaining a reasonably accurate description of the electronic structure (in this case, CAM-B3LYP/6-31G(∗∗)). In total, we have identified 3792 promising candidate fluorophores from a chemical space containing 1.26 × 10(6) molecules. This required performing electronic structure calculations on only 7518 molecules, a small fraction of the full space. Several novel classes of molecules which show promise as fluorophores are presented.

Unphysical spatial symmetry breaking in multiconfigurational self-consistent field calculations can lead to undesirable artifacts in the potential energy surfaces and electronic properties of molecules. Herein, we report several examples of such symmetry breaking in calculations of the excited states of small semiconductor clusters and related molecules at the state-averaged complete active space self-consistent field (SA-CASSCF) level of theory. A multireference approach is proposed to reduce its incidence: the singly excited active space complete active space configuration interaction (SEAS-CASCI) method. In SEAS-CASCI, the orbitals are determined by variationally minimizing an energy expression that does not depend on the off-diagonal Hamiltonian matrix elements which drive symmetry breaking at the SA-CASSCF level of theory. By application to several highly symmetric molecules, SEAS-CASCI is demonstrated to reduce the propensity for unphysical spatial symmetry breaking and eliminate resulting errors in the potential energy surfaces and molecular properties relative to the SA-CASSCF description. The SEAS method is also found to eliminate unphysical wavefunction distortion in asymmetric molecules. Finally, SEAS-CASCI is demonstrated to accurately describe the biradicaloid region of the potential energy surface of ethylene.