Subscribe to the gold package and get unlimited access to Shamra Academy
Register a new userSystematic improvement of molecular excited state calculations by inclusion of nuclear quantum motion: a mode-resolved picture and the effect of molecular size
178
0
0.0
(
0
)
Ask ChatGPT about the research
No Arabic abstract
The energies of molecular excited states arise as solutions to the electronic Schr{o}dinger equation and are often compared to experiment. At the same time, nuclear quantum motion is known to be important and to induce a red-shift of excited state energies. However, it is thus far unclear whether incorporating nuclear quantum motion in molecular excited state calculations leads to a systematic improvement of their predictive accuracy, making further investigation necessary. Here we present such an investigation by employing two first-principles methods for capturing the effect of quantum fluctuations on excited state energies, which we apply to the Thiel set of organic molecules. We show that accounting for zero-point motion leads to much improved agreement with experiment, compared to `static calculations which only account for electronic effects, and the magnitude of the red-shift can become as large as 1.36 eV. Moreover, we show that the effect of nuclear quantum motion on excited state energies largely depends on the molecular size, with smaller molecules exhibiting larger red-shifts. Our methodology also makes it possible to analyze the contribution of individual vibrational normal modes to the red-shift of excited state energies, and in several molecules we identify a limited number of modes dominating this effect. Overall, our study provides a foundation for systematically quantifying the shift of excited state energies due to nuclear quantum motion, and for understanding this effect at a microscopic level.
rate research
Read More
Second-Harmonic Scatteringh (SHS) experiments provide a unique approach to probe non-centrosymmetric environments in aqueous media, from bulk solutions to interfaces, living cells and tissue. A central assumption made in analyzing SHS experiments is that the each molecule scatters light according to a constant molecular hyperpolarizability tensor $boldsymbol{beta}^{(2)}$. Here, we investigate the dependence of the molecular hyperpolarizability of water on its environment and internal geometric distortions, in order to test the hypothesis of constant $boldsymbol{beta}^{(2)}$. We use quantum chemistry calculations of the hyperpolarizability of a molecule embedded in point-charge environments obtained from simulations of bulk water. We demonstrate that both the heterogeneity of the solvent configurations and the quantum mechanical fluctuations of the molecular geometry introduce large variations in the non-linear optical response of water. This finding has the potential to change the way SHS experiments are interpreted: in particular, isotopic differences between H$_2$O and D$_2$O could explain recent second-harmonic scattering observations. Finally, we show that a simple machine-learning framework can predict accurately the fluctuations of the molecular hyperpolarizability. This model accounts for the microscopic inhomogeneity of the solvent and represents a first step towards quantitative modelling of SHS experiments.
MOLSCAT is a general-purpose program for quantum-mechanical calculations on nonreactive atom-atom, atom-molecule and molecule-molecule collisions. It constructs the coupled-channel equations of atomic and molecular scattering theory, and solves them by propagating the wavefunction or log-derivative matrix outwards from short range to the asymptotic region. It then applies scattering boundary conditions to extract the scattering matrix (S matrix). Built-in coupling cases include atom + rigid linear molecule, atom + vibrating diatom, atom + rigid symmetric top, atom + asymmetric or spherical top, rigid diatom + rigid diatom, rigid diatom + asymmetric top, and diffractive scattering of an atom from a crystal surface. Interaction potentials may be specified either in program input (for simple cases) or with user-supplied routines. For the built-in coupling cases, MOLSCAT can loop over partial wave (or total angular momentum) to calculate elastic and inelastic cross integral sections and spectroscopic line-shape cross sections. Post-processors are available to calculate differential cross sections, transport, relaxation and Senftleben-Beenakker cross sections, and to fit the parameters of scattering resonances. MOLSCAT also provides an interface for plug-in routines to specify coupling cases (Hamiltonians and basis sets) that are not built in; plug-in routines are supplied to handle collisions of a pair of alkali-metal atoms with hyperfine structure in an applied magnetic field. For low-energy scattering, MOLSCAT can calculate scattering lengths and effective ranges and can locate and characterize scattering resonances as a function of an external variable such as the magnetic field.
Implicit electron-density solvation models based on joint density-functional theory offer a computationally efficient solution to the problem of calculating thermodynamic quantities of solvated systems from firstprinciples quantum mechanics. However, despite much recent interest in such models, to date the applicability of such models in the plane-wave context to non-aqueous solvents has been limited because the determination of the model parameters requires fitting to a large database of experimental solvation energies for each new solvent considered. This work presents an alternate approach which allows development of new iso-density models for a large class of protic and aprotic solvents from only simple, single-molecule ab initio calculations and readily available bulk thermodynamic data.
While Diffusion Monte Carlo (DMC) is in principle an exact stochastic method for textit{ab initio} electronic structure calculations, in practice the fermionic sign problem necessitates the use of the fixed-node approximation and trial wavefunctions with approximate nodes (or zeros) must be used. This approximation introduces a variational error in the energy that potentially can be tested and systematically improved. Here, we present a computational method that produces trial wavefunctions with systematically improvable nodes for DMC calculations of periodic solids. These trial wavefunctions are efficiently generated with the configuration interaction using a perturbative selection made iteratively (CIPSI) method. A simple protocol in which both exact and approximate results for finite supercells are used to extrapolate to the thermodynamic limit is introduced.
The possibility of using quantum computers for electronic structure calculations has opened up a promising avenue for computational chemistry. Towards this direction, numerous algorithmic advances have been made in the last five years. The potential of quantum annealers, which are the prototypes of adiabatic quantum computers, is yet to be fully explored. In this work, we demonstrate the use of a D-Wave quantum annealer for the calculation of excited electronic states of molecular systems. These simulations play an important role in a number of areas, such as photovoltaics, semiconductor technology and nanoscience. The excited states are treated using two methods, time-dependent Hartree-Fock (TDHF) and time-dependent density-functional theory (TDDFT), both within a commonly used Tamm-Dancoff approximation (TDA). The resulting TDA eigenvalue equations are solved on a D-Wave quantum annealer using the Quantum Annealer Eigensolver (QAE), developed previously. The method is shown to reproduce a typical basis set convergence on the example H$_2$ molecule and is also applied to several other molecular species. Characteristic properties such as transition dipole moments and oscillator strengths are computed as well. Three potential energy profiles for excited states are computed for NH$_3$ as a function of the molecular geometry. Similar to previous studies, the accuracy of the method is dependent on the accuracy of the intermediate meta-heuristic software called qbsolv.
Log in to be able to interact and post comments
comments
Fetching comments
Sign in to be able to follow your search criteria
