Analytical derivative couplings within the framework of time-dependent density functional theory coupled with conductor-like polarizable continuum model: Formalism, implementation, and applications

Huang, Xunkun; Pei, Zheng; Liang, WanZhen

doi:10.1063/5.0130617

Cited by 3 publications

(1 citation statement)

References 92 publications

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“…Analytic NACs have been created for CIS, spin-flip CIS, and time-dependent density-functional theory with the conductor-like PCM . Coupled cluster approaches have had analytic NACs derived and implemented. − An efficient method of calculating overlaps between wave functions has been created that can be used for fully numerical NACs, and artificial neural networks have also been trained to predict NACs as part of surface hopping molecular dynamics .…”

Section: Introductionmentioning

confidence: 99%

Analytic Non-adiabatic Couplings for Selected Configuration Interaction via Approximate Degenerate Coupled Perturbed Hartree–Fock

Coe

2023

J. Chem. Theory Comput.

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We use degenerate perturbation theory and assume that for degenerate pairs of orbitals, the coupled perturbed Hartree–Fock coefficients are symmetric in the degenerate basis to show U c d X A = prefix− 1 2 S d c X A is the only modification needed in the original molecular orbital basis. This enables us to develop efficient and accurate analytic nonadiabatic couplings between electronic states for selected configuration interactions (CIs). Even when the states belong to different irreducible representations, degenerate orbital pairs cannot be excluded by symmetry. For various excited states of carbon monoxide and trigonal planar ammonia, we benchmark the method against the full CI and find it to be accurate. We create a semi-numerical approach and use it to show that the analytic approach is correct even when a high-symmetry structure is distorted to break symmetry so that near degeneracies in orbitals occur. For a range of geometries of trigonal planar ammonia, we find that the analytic non-adiabatic couplings for selected CI can achieve sufficient accuracy using a small fraction of the full CI space.

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Section: Introductionmentioning

confidence: 99%

Analytic Non-adiabatic Couplings for Selected Configuration Interaction via Approximate Degenerate Coupled Perturbed Hartree–Fock

Coe

2023

J. Chem. Theory Comput.

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Understanding chemical properties, formation mechanism, and cation-π interaction of dibenzocines from DFT calculations

Saeidian,

Mirjafary,

Bakhtiari

et al. 2024

Journal of Organometallic Chemistry

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Dissecting the ingredients of optimally tuned range-separated hybrid models for reliable description of non-adiabatic couplings

Izadkhast

2023

The Journal of Chemical Physics

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Perusing the non-radiative processes requires a reliable prediction of non-adiabatic couplings (NACs) describing the interaction of two Born–Oppenheimer surfaces. In this regard, the development of appropriate and affordable theoretical methods that accurately account for the NAC terms between different excited-states is desirable. In this work, we develop and validate several variants of the optimally tuned range-separated hybrid functionals (OT-RSHs) for investigating NACs and related properties, such as excited states energy gaps and NAC forces, within the time-dependent density functional theory framework. Particular attention is paid to the influence of the underlying density functional approximations (DFAs), the short- and long-range Hartree–Fock (HF) exchange contributions, and the range-separation parameter. Considering several radical cations and sodium-doped ammonia clusters with the available reference data for the NACs and related quantities as the working models, we have evaluated the applicability and accountability of the proposed OT-RSHs. The obtained results unveil that any combination of the ingredients in the proposed models is not proper for describing the NACs, but a particular compromise among the involved parameters is needed to achieve reliable accuracy. Scrutinizing the results of our developed methods, the OT-RSHs based on the PBEPW91, BPW91, and PBE exchange and correlation DFAs, including about 30% HF exchange at the short-range regime, appeared to be the best performers. We also find that the newly developed OT-RSHs with correct asymptotic exchange-correlation potential have superior performances as compared to their standard counterparts with the default parameters and many earlier hybrids with both fixed and interelectronic distance-dependent HF exchange. The recommended OT-RSHs in this study can hopefully be applicable as computationally efficient alternatives to the expensive wave function-based methods for the systems prone to non-adiabatic properties as well as to screen out the novel candidates prior to their challenging synthesis.

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Analytical derivative couplings within the framework of time-dependent density functional theory coupled with conductor-like polarizable continuum model: Formalism, implementation, and applications

Cited by 3 publications

References 92 publications

Analytic Non-adiabatic Couplings for Selected Configuration Interaction via Approximate Degenerate Coupled Perturbed Hartree–Fock

Analytic Non-adiabatic Couplings for Selected Configuration Interaction via Approximate Degenerate Coupled Perturbed Hartree–Fock

Understanding chemical properties, formation mechanism, and cation-π interaction of dibenzocines from DFT calculations

Dissecting the ingredients of optimally tuned range-separated hybrid models for reliable description of non-adiabatic couplings

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