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Correspondence between electronic structure calculations and simulations:: nonadiabatic dynamics in CS2

Correspondence between electronic structure calculations and simulations:: nonadiabatic dynamics in CS2
Correspondence between electronic structure calculations and simulations:: nonadiabatic dynamics in CS2
The choice of ab initio electronic structure method is an important factor in determining the fidelity of nonadiabatic dynamics simulations. We present an in-depth comparison of two simulations of photodissociation in the CS2 molecule following excitation to the 1 1^B_2 state. The simulations account for nonadiabatic and spin-orbit coupling, and are performed using the SHARC surface-hopping approach combined with state-averaged SA8-CASSCF(8,6)/SVP and SA8-CASSCF(10,8)/SVP {\it{ab initio}} calculations, with additional reference calculations at the MRCI(14,10)/aug-cc-pvTZ level. The relative performance and veracity of the simulations can be assessed by inspection of the potential energy curves along specific coordinates. The simulations demonstrate direct competition between internal conversion and intersystem crossing, with strong correlation between molecular geometry, electronic state density, and dynamics.
1463-9076
Bellshaw, Darren
48dd9375-5b86-4d80-a00a-e5552cbd910c
Minns, Russell
85280db4-c5a6-4a4c-82fe-75693c6a6045
Kirrander, Adam
bf3ed07d-dbe0-4f83-bb97-a0f9c27363ca
Bellshaw, Darren
48dd9375-5b86-4d80-a00a-e5552cbd910c
Minns, Russell
85280db4-c5a6-4a4c-82fe-75693c6a6045
Kirrander, Adam
bf3ed07d-dbe0-4f83-bb97-a0f9c27363ca

Bellshaw, Darren, Minns, Russell and Kirrander, Adam (2018) Correspondence between electronic structure calculations and simulations:: nonadiabatic dynamics in CS2. Physical Chemistry Chemical Physics. (doi:10.1039/C8CP05693E).

Record type: Article

Abstract

The choice of ab initio electronic structure method is an important factor in determining the fidelity of nonadiabatic dynamics simulations. We present an in-depth comparison of two simulations of photodissociation in the CS2 molecule following excitation to the 1 1^B_2 state. The simulations account for nonadiabatic and spin-orbit coupling, and are performed using the SHARC surface-hopping approach combined with state-averaged SA8-CASSCF(8,6)/SVP and SA8-CASSCF(10,8)/SVP {\it{ab initio}} calculations, with additional reference calculations at the MRCI(14,10)/aug-cc-pvTZ level. The relative performance and veracity of the simulations can be assessed by inspection of the potential energy curves along specific coordinates. The simulations demonstrate direct competition between internal conversion and intersystem crossing, with strong correlation between molecular geometry, electronic state density, and dynamics.

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c8cp05693e - Accepted Manuscript
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More information

Accepted/In Press date: 29 November 2018
e-pub ahead of print date: 29 November 2018

Identifiers

Local EPrints ID: 426687
URI: https://eprints.soton.ac.uk/id/eprint/426687
ISSN: 1463-9076
PURE UUID: 6636bd7b-4171-43c3-9ee5-8d9bf5c3d3c1
ORCID for Russell Minns: ORCID iD orcid.org/0000-0001-6775-2977

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Date deposited: 10 Dec 2018 17:31
Last modified: 14 Mar 2019 01:36

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