Intensities of Hot-Band Transitions: HCN Hot Bands

Maki, A. G.; Quapp, Wolfgang; Klee, S.

doi:10.1006/jmsp.1995.1130

Cited by 49 publications

(67 citation statements)

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“…2 we present an overview of the quite dense emission spectrum of the 2 region. The band center of the 2 Figure 3 shows some Q branches in the 2 region. The assignment of transitions was aided by the Giessen Loomis-Wood program (19).…”

Section: Assignment Of the Transitionsmentioning

confidence: 98%

“…Parallel to the analysis of the D 13 C 15 N measurements, we have made similar analyses for DCN, D 13 C 14 N, and D 12 C 15 N. The data for the latter three isotopomers came from room temperature absorption measurements, some of which were not intentionally enriched in deuterium (1)(2)(3)(4)(5).…”

Section: Introductionmentioning

confidence: 98%

“…We also report room temperature absorption measurements of this and other isotopomers of DCN. The emission spectrum gives many transitions to previously unobserved bending states up to v 2 ϭ 12 and some combinations of the CN stretch mode, 3 , with various quanta of the bending mode, 2 . Such high bending states can be observed because of the vibrational dependence of the harmonic oscillator transition moment, which has been described by Maki et al (3).…”

Section: Introductionmentioning

confidence: 99%

“…The spectrum of hydrogen cyanide, HCN, and that of its isotopomers has been measured extensively (1)(2)(3)(4)(5) because it is very simple and yet it shows many features that are of interest from a theoretical point of view. The spectrum is also the basis for comparison with ab initio calculations (6 -8).…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Climbing the Bending Vibrational Ladder in D13C15N by Hot Gas Emission Spectroscopy

Quapp

Hirsch

Mellau

et al. 1999

Journal of Molecular Spectroscopy

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Section: Assignment Of the Transitionsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Climbing the Bending Vibrational Ladder in D13C15N by Hot Gas Emission Spectroscopy

Quapp

Hirsch

Mellau

et al. 1999

Journal of Molecular Spectroscopy

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“…[41][42][43][44][45][46][47][48][49][50][51][52][53][54][55][56] The work of Lehmann et al 57 is the starting point for experiments designed to record spectra for the detection of the highly excited rovibrational states of the [H,C,N] molecular system. [58][59][60][61][62][63][64][65][66][67][68][69][70][71][72][73][74] Over time the number of the detected band centers increased steadily. The sensitivity of all these experiments regarding the detection of highly excited bending states and highly excited rotational states was relatively low so that each work described only a small part of the overall rovibrational eigenenergy structure.…”

Section: Introductionmentioning

confidence: 99%

Complete experimental rovibrational eigenenergies of HCN up to 6880 cm−1 above the ground state

Mellau

2011

The Journal of Chemical Physics

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The [H,C,N] molecular system is a very important model system to many fields of chemical physics and the experimental characterization of highly excited vibrational states of this molecular system is of special interest. This paper reports the experimental characterization of all 3822 eigenenergies up to 6880 cm −1 relative to the ground state in the HCN part of the potential surface using high temperature hot gas emission spectroscopy. The spectroscopic constants for the first 71 vibrational states including highly excited bending vibrations up to v 2 = 10 are reported. The perturbed eigenenergies for all 20 rotational perturbations in the reported eigenenergy range have been determined. The 11 070 eigenenergies up to J = 90 for the first 123 vibrational substates are included as supplement to this paper. We show that a complete ab initio rovibrational analysis for a polyatomic molecule is possible. Using such an analysis we can understand the molecular physics behind the Schrödinger equation for problems for which perturbation theoretical calculations are no more valid. We show that the vibrational structure of the linear HCN molecule persists approximately up to the isomerization barrier and only above the barrier the accommodation of the vibrational states to the double well structure of the potential takes place.

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Transition state theory with Tsallis statistics

Quapp

Zech

2009

J Comput Chem

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We discuss the rate of an elementary chemical reaction. We use the reaction path and especially its saddle point on the potential energy surface. The reaction path connects reactant and product of a reaction over the transition state (TS). Usually, the TS is assumed near or at the single saddle point of the reaction path. By means of comparison of the statistics of states at the reactant and at the TS, one can estimate the reaction rate by the Eyring theory. We propose to use the Tsallis statistics at the TS, a statistics of seldom accidents. Thus, we propose to generalize the well-known Boltzmann-Gibbs statistics, which is the limiting case of the Tsallis statistics. We use features of this nonextensive thermostatistics. The basic properties of the statistics are used to derive (approximated) partition functions, and they are applied on reaction rates. The approximation includes a factorization of the partition functions. The theory is applied to HCN isomerization to HNC, and to the reaction H(2) + CN --> H + HCN. It allows an accordance with experimental estimations of the reaction rates.

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Intensities of Hot-Band Transitions: HCN Hot Bands

Cited by 49 publications

References 0 publications

Climbing the Bending Vibrational Ladder in D13C15N by Hot Gas Emission Spectroscopy

Climbing the Bending Vibrational Ladder in D13C15N by Hot Gas Emission Spectroscopy

Complete experimental rovibrational eigenenergies of HCN up to 6880 cm−1 above the ground state

Transition state theory with Tsallis statistics

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