An exploration of electronic structure and nuclear dynamics in tropolone: II. The à B12 (π∗π) excited state
作者： Lori A. Burns , Daniel Murdock , Patrick H. Vaccaro
DOI: 10.1063/1.3089722
关键词: Time-dependent density functional theory 、 Bond length 、 Molecular electronic transition 、 Ground state 、 Excited state 、 Configuration interaction 、 Atomic physics 、 Chemistry 、 Electronic structure 、 Density functional theory
摘要: The first excited singlet state of tropolone (A (1)B(2)) and the attendant pi(*)<--pi electronic transition have been examined computationally by applying several quantum chemical treatments built upon aug-cc-pVDZ basis set, including time-dependent density functional theory (TDDFT/B3LYP), configuration interaction singles with perturbative corrections [CIS CIS(D)], equation-of-motion coupled-cluster schemes [EOM-CCSD CR-EOMCCSD(T)]. As in case X (1)A(1) ground [L. A. Burns, D. Murdock, P. H. Vaccaro, J. Chem. Phys. 124, 204307 (2006)], geometry optimization procedures harmonic force-field calculations predict electronically potential surface to support a global minimum-energy rigorously planar (C(s)) symmetry. Minimal Hartree-Fock (HF/CIS) density-functional (DFT/TDDFT) approaches yield inconsistent results for A (1)B(2) manifolds; however, (CCSD/EOM-CCSD) methods give fully relaxed proton-transfer barrier heights DeltaE(pt) (X)=3296.1 cm(-1) (A)=1270.6 that are accordance experimentally observed increase vibrationless tunneling splitting excitation. Detailed analyses show this reduction stems from variety complementary factors, most notably an overall contraction reaction site (whereby equilibrium O...O donor-acceptor distance decreases 2.53 2.46 A) concomitant shortening intramolecular hydrogen bond. Further refinement energies through single-point triples [CR-EOMCCSD(T)] leads 1316.1 as best current estimate (A). Direct comparison lowest-lying out-of-plane torsional mode [nu(39)(a(2))] reveals its disparate nature (cf. nu(39) (X)=101.2 (A)=42.0 cm(-1)) mediates vibrational-averaging effects which can account inertial defects extracted rotationally resolved spectroscopic measurements.
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