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Excited state electronic structure of dimethyl disulfide involved in photodissociation at ∼200 nm

Journal Article · · Physical Chemistry Chemical Physics
DOI:https://doi.org/10.1039/d4cp02505a· OSTI ID:2587648
 [1];  [1];  [1];  [1]
  1. Sandia National Laboratories (SNL-CA), Livermore, CA (United States)
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Dimethyl disulfide (DMDS), one of the smallest organic molecules with an S–S bond, serves as a model system for understanding photofragmentation in polypeptides and proteins. Prior studies of DMDS photodissociation excited at ∼266 nm and ∼248 nm have elucidated the mechanisms of S–S and C–S bond cleavage, which involve the lowest excited electronic states S1 and S2. Far less is known about the dissociation mechanisms and electronic structure of relevant excited states of DMDS excited at ∼200 nm. Herein we present calculations of the electronic structure and properties of electronic states S1–S6 accessed when DMDS is excited at ∼200 nm. Our analysis includes a comparison of theoretical and experimental UV spectra, as well as theoretically predicted one-dimensional cuts through the singlet and triplet potential energy surfaces along the S–S and C–S bond dissociation coordinates. Finally, we present calculations of spin–orbit coupling constants at the Franck–Condon geometry to assess the likelihood of ultrafast intersystem crossing. We show that choosing an accurate yet computationally efficient electronic structure method for calculating the S0–S6 potential energy surfaces along relevant dissociation coordinates is challenging due to excited states with doubly excited character and/or mixed Rydberg-valence character. Our findings demonstrate that the extended multi-state complete active space second-order perturbation theory (XMS-CASPT2) balances this computational efficiency and accuracy, as it captures both the Rydberg character of states in the Franck–Condon region and multiconfigurational character toward the bond-dissociation limits. In conclusion, we compare the performance of XMS-CASPT2 to a new variant of equation of motion coupled cluster theory with single, double, and perturbative triple corrections, EOM-CCSD(T)(a)*, finding that EOM-CCSD(T)(a)* significantly improves the treatment of doubly excited states compared to EOM-CCSD, but struggles to quantitatively capture asymptotic energies along bond dissociation coordinates for these states.
Research Organization:
Sandia National Laboratories (SNL-CA), Livermore, CA (United States)
Sponsoring Organization:
National Energy Research Scientific Computing Center (NERSC); USDOE; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
Grant/Contract Number:
AC02-05CH11231; NA0003525
OSTI ID:
2587648
Alternate ID(s):
OSTI ID: 2440078
Journal Information:
Physical Chemistry Chemical Physics, Journal Name: Physical Chemistry Chemical Physics Journal Issue: 36 Vol. 26; ISSN 1463-9076; ISSN 1463-9084
Publisher:
Royal Society of Chemistry (RSC)Copyright Statement
Country of Publication:
United States
Language:
English

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Figures / Tables (13)

FIG. 4(p. 13)figure FIG. 4
FIG. 7(p. 19)figure FIG. 7
TABLE III(p. 17)table TABLE III
FIG. 1(p. 9)figure FIG. 1
FIG. 3(p. 12)figure FIG. 3
FIG. 9(p. 23)figure FIG. 9
FIG. 10(p. 24)figure FIG. 10
FIG. 6(p. 18)figure FIG. 6
TABLE II(p. 10)table TABLE II
FIG. 2(p. 11)figure FIG. 2
FIG. 5(p. 14)figure FIG. 5
FIG. 8(p. 22)figure FIG. 8
TABLE I(p. 10)table TABLE I

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