Abstract
Time-resolved resonance Raman (TR3) spectroscopy has been used to study the structure of the triplet excited state of bromanil. These experimental results were then simulated using parameters from density functional theoretical (DFT) calculations and wave packet dynamics, in order to understand the structure and mode-specific displacements of the resonant excited state. The transition dipole moments and the energy separation of the T1 and Tn states were obtained from time-dependent DFT calculations. We have demonstrated application of the technique to tetrabromo-p-benzoquinone. From our calculations, the observed T1→Tn absorption spectrum has been assigned to the Bg3→3Bu transition. The geometry has been optimized for the resonant higher triplet state, Tn, and is found to be in good agreement with the predictions of the wave packet dynamical simulations. Mode-specific displacements of the triplet state geometry have been obtained from simulations and these have been rationalized with respect to the molecular orbital involved. Thus, we have demonstrated that from the simulations of the experimental TR3 spectral data, valuable additional information can be derived on the structure of the transient states that may then be used for elucidation of structure-reactivity correlation in the future.
Keywords
Excited stateDipoleResonance (particle physics)Wave packetAtomic physicsRaman spectroscopyTriplet stateMolecular physicsDensity functional theoryChemistrySpectral linePhysicsComputational chemistryQuantum mechanics
Affiliated Institutions
Related Publications
Spin−Orbit Coupling and Intersystem Crossing in Conjugated Polymers: A Configuration Interaction Description
Configuration−interaction calculations are performed to describe the singlet and triplet excited states of oligothiophene and oligo(phenylene ethynylene) conjugated chains. Inte...
Theoretical potential energy function and rovibronic spectrum of CO+2(<i>X</i> 2Π<i>g</i>)
For the electronic ground state of CO+2 the three-dimensional potential energy, electric dipole, and transition moment functions have been calculated from highly correlated mult...
Threshold and resonance phenomena in ultracold ground-state collisions
We study the magnetic-field dependence of the cross sections for elastic and inelastic collisions of pairs of ultracold cesium atoms in a magnetic trap, calculated with the coup...
CP2K: An electronic structure and molecular dynamics software package - Quickstep: Efficient and accurate electronic structure calculations
CP2K is an open source electronic structure and molecular dynamics software package to perform atomistic simulations of solid-state, liquid, molecular, and biological systems. I...
Multireference configuration interaction calculations of the low-lying electronic states of ClO2
Using extensive internally contracted multireference configuration interaction wave functions and large basis sets, near-equilibrium potential energy functions for the first fou...
Publication Info
- Year
- 2001
- Type
- article
- Volume
- 115
- Issue
- 13
- Pages
- 6106-6114
- Citations
- 13
- Access
- Closed
External Links
Social Impact
Altmetric
PlumX Metrics
Social media, news, blog, policy document mentions
Citation Metrics
13
OpenAlex
Cite This
Mrinalini Puranik,
Siva Umapathy,
J. G. Snijders
et al.
(2001).
Structure of the triplet excited state of bromanil from time-resolved resonance Raman spectra and simulation.
The Journal of Chemical Physics
, 115
(13)
, 6106-6114.
https://doi.org/10.1063/1.1398304
Identifiers
- DOI
- 10.1063/1.1398304