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Journal ArticleDOI

Laser induced dispersed fluorescence spectra of jet cooled NO2: The complete set of vibrational levels up to 10 000 cm−1 and the onset of the X̃ 2A1–Ã 2B2 vibronic interaction

A. Delon, +1 more
- 15 Oct 1991 - 
- Vol. 95, Iss: 8, pp 5686-5700
TLDR
In this article, the laser induced dispersed fluorescence spectra (L.I.D.F.S) of jet cooled NO2 molecules in emission from 11 different vibronic levels located between 22.006 and 23.625 cm−1 was recorded.
Abstract
The laser induced dispersed fluorescence spectra (L.I.D.F.S.) of jet cooled NO2 molecules in emission from 11 different vibronic levels located between 22 006 and 23 625 cm−1 was recorded. The corresponding variety of Franck–Condon accesses has allowed the observation of the complete set of the 191 lowest vibrational levels of the X 2A1 ground state, located up to 10 000 cm−1. The vibrational band origins were measured to within typically 0.3 cm−1, assigned (n1, n2, n3), and fitted with a 24 coefficient Dunham expansion giving a typical residual error of 0.5 cm−1. Furthermore, the vibrationless A 2B2 level has probably also been observed at 9737 cm−1. A perturbative model of the X 2A1–A 2B2 vibronic interaction has been used in order to calculate the energy shift of the high vibrational levels (around 10 000 cm−1) of the X 2A1 state.

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Citations
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Journal ArticleDOI

A new table-direct configuration interaction method for the evaluation of Hamiltonian matrix elements in a basis of linear combinations of spin-adapted functions

TL;DR: In this paper, a new table-direct CI (TDCI) scheme for the direct computation of Hamiltonian matrix elements whose basis functions are linear combinations of spin-adapted functions ψα is presented, in which the explicit calculation and storage of the Hamiltonians matrix H in the basis {ψα} is avoided.
Journal ArticleDOI

HCP CPH ISOMERIZATION: Caught in the Act

TL;DR: The vibrational spectrum of phosphaethyne, HCP, in its electronic ground state, as revealed by complementary experimental and theoretical examinations is discussed, which provides a detailed spectroscopic picture of the breaking of one bond and the formation of a new one.
Journal ArticleDOI

Sums and densities of fully coupled anharmonic vibrational states: a comparison of three practical methods.

TL;DR: The Wang-Landau algorithm is shown to be practical and reasonably accurate for molecules containing approximately 4 or more atoms, where the practical size limit is currently on the order of perhaps 50 atoms and the errors depend mostly on the average number of stochastic samples per energy bin.
Journal ArticleDOI

The monoenergetic unimolecular reaction of expansion‐cooled NO2: NO product state distributions at excess energies 0–3000 cm−1

TL;DR: In this article, the vibrational, rotational, and electronic distributions of NO(X 2 Π 1/2,3/2) were derived from monoenergetic unimolecular reactions of expansion-cooled NO2.
Journal ArticleDOI

Probing the NO2→NO+O transition state via time resolved unimolecular decomposition

TL;DR: In this paper, the photo-initiated NO2 unimolecular decomposition rates were measured for both expansion cooled and room temperature samples, where the molecules were excited by 375-402 nm tunable sub-picosecond pulses having bandwidths ≥20 cm−1 to levels which are known to be thorough admixtures of the 2B2 electronically excited state and the 2A1 ground electronic state.
References
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Journal ArticleDOI

Random matrix physics: Spectrum and strength fluctuations

TL;DR: In this article, it was shown that the general nature of deviations from uniformity in the spectrum of a complicated nucleus is essentially the same in all regions of the spectrum and over the entire Periodic Table.
Journal ArticleDOI

The fluorescence excitation spectrum of rotationally cooled NO2

TL;DR: In this article, the fluorescence excitation spectrum of NO2 was measured in the region 5708-6708 A using a tuneable dye laser as an excitation source.
Journal ArticleDOI

The electronic structure of nitrogen dioxide. I. Multiconfiguration self‐consistent‐field calculation of the low‐lying electronic states

TL;DR: In this article, a multiconfiguration self-consistent field (MC-SCF) wavefunctions have been computed for the low-lying X 2A1, A 2B2, B 2B1, C 2A2, 4B2 and 2Σ+g electronic states of NO2.
Journal ArticleDOI

The two lowest energy 2A′ states of NO2

TL;DR: In this article, the 2A1 ground state of NO2 and the so-called 2B2 excited state are shown to form a strongly coupled pair of 2A′ states when asymmetric distortion is considered.
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