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

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Choosing the right ab initio electronic structure method is crucial for accurate nonadiabatic dynamics simulations. This study compares two methods for CS2 photodissociation, revealing competition between internal conversion and intersystem crossing.

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Area of Science:

  • Chemical Physics
  • Computational Chemistry
  • Quantum Dynamics

Background:

  • Accurate nonadiabatic dynamics simulations are essential for understanding molecular photochemistry.
  • The choice of ab initio electronic structure method significantly impacts simulation fidelity.
  • Photodissociation of CS2 provides a benchmark system for studying complex electronic transitions.

Purpose of the Study:

  • To compare the performance of two state-averaged complete active space self-consistent field (SA-CASSCF) methods for simulating CS2 photodissociation.
  • To investigate the influence of nonadiabatic and spin-orbit coupling on the dynamics.
  • To assess the reliability of different ab initio methods in capturing competing decay pathways.

Main Methods:

  • Utilized the SHARC (Surface-hopping including ARbitrary Couplings) surface-hopping approach.
  • Employed state-averaged SA8-CASSCF(8,6)/SVP and SA8-CASSCF(10,8)/SVP ab initio calculations.
  • Performed reference calculations using Multi-Reference Configuration Interaction (MRCI) with Davidson correction (MRCI(14,10)/aug-cc-pvTZ).

Main Results:

  • Simulations revealed a direct competition between internal conversion and intersystem crossing in CS2 photodissociation.
  • Strong correlations were observed between molecular geometry, electronic state density, and the resulting dynamics.
  • Potential energy curves along specific coordinates were used to assess simulation accuracy.

Conclusions:

  • The fidelity of nonadiabatic dynamics simulations is highly dependent on the chosen ab initio electronic structure method.
  • SA-CASSCF methods, when appropriately chosen, can reasonably capture complex dynamics involving internal conversion and intersystem crossing.
  • Understanding the interplay between geometry, state density, and dynamics is key for accurate photochemical simulations.