Photoexcitation of the NaKCl Reaction Complex

Maguire, T. C.; Brooks, Philip R.; Curl, R. F.

doi:10.1103/physrevlett.50.1918

Cited by 53 publications

(4 citation statements)

References 9 publications

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“…Emission from molecules in the process of falling apart [14][15][16] and emission from reactive collisions [8,17,18] are well documented. The essential difference is that these previous studies refer to emission from electronically excited states to the ground state or to absorption in the opposite direction e.g., [18,19]. Here we are concerned with emission (or absorption) resulting from the motion of the nuclei on the ground electronic state.…”

Section: Introductionmentioning

confidence: 99%

Probing electronic rearrangement during chemical reactions

et al. 2005

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During a chemical reaction the electronic structure of the reactants reforms to the structure of the products. In the simplest case, an old bond is broken and simultaneously a new bond is formed. Even when this change occurs adiabatically, meaning that the electronic charge distribution tracks the motion of the nuclei without change in its quantum state, there is a displacement of charge, particularly so if there is a switch from a covalent to an ionic bonding. This reorganization can be probed by light emitted during the very collision. The F + H 2 reaction is used as a computational example.

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Section: Introductionmentioning

confidence: 99%

Probing electronic rearrangement during chemical reactions

et al. 2005

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“…Among the reactions investigated was that of K(42S) atoms with NaCl using excitation with 660-nm laser radiation (Figure 16b) in a crossed molecular beam experiment. 79 As the reaction partners approach, the particle states mutually "disturb" one another and their energy changes until the laser is finally resonant with the Na*(32P)-KCl potential curve. Then electronic excitation occurs and light emission from Na*(32P) at 589 nm is observed.…”

Section: Electronic Excitationmentioning

confidence: 99%

Laser stimulation and observation of bimolecular reactions

Wolfrum¹

1986

J. Phys. Chem.

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“…The central importance of transition states ͑defined here and in the recent literature of this field as critical species intermediate between reactants and products, and thus not limited to the saddle points that play the critical role in conventional transition state theory or activated complex theory͒ has resulted in the emergence of the field of ''transition state spectroscopy,'' 1,2 in which optical probes interact with the evolving transition state so as to characterize its successive internuclear and electronic configurations. Since the early observation of transition states in emission [3][4][5][6][7][8][9] and absorption, [10][11][12][13][14][15][16][17] there have been important recent developments, among which we note the work of the Neumark, group which has observed transition state quantum structure by photodetachment of negative ions, [18][19][20][21][22][23][24] and the real-time clocking of the evolution of transition states using femtosecond lasers, pre-eminentally by Zewail and his group. 2,[25][26][27][28][29][30][31][32][33][34] Recent work in one of our laboratories [35][36][37][38][39][40] uses a method for accessing the transition state first proposed by Soep and co-workers [41]…”

Section: Introductionmentioning

confidence: 99%

The photoabsorption spectrum of Na⋯FH van der Waals molecule: Comparison of theory and experiment for a harpooning reaction studied by transition state spectroscopy

Topaler

Truhlar

Chang

et al. 1998

The Journal of Chemical Physics

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Articles you may be interested inAb initio potential energy surfaces, total absorption cross sections, and product quantum state distributions for the low-lying electronic states of N 2 O J. Chem. Phys. 122, 054305 (2005); 10.1063/1.1830436Erratum: "Photodissociation of LiFH and NaFH van der Waals complexes: A semiclassical trajectory study" [J.The photodissociation of Na¯FH van der Waals molecules in the 1.5-2.3 eV energy region is a very interesting system for transition state spectroscopy, because the potential energy surfaces for electronically excited states funnel the system down to the ground electronic state in a critical region where detailed features of the potential energy surfaces may be important in determining the branching probability between the harpooning reaction to form NaF or the dissociative E→V energy transfer process to form vibrationally excited HF. We used an analytic representation, reported earlier, of the potential surfaces for the two lowest AЈ electronic states of NaFH as well as separable fits for two higher excited potential surfaces to simulate the experimental photodepletion spectrum of the Na¯FH van der Waals molecule. Franck-Condon analysis was performed for the X 2 AЈ→Ã 2 AЈ, X 2 AЈ→B 2 AЉ, and X 2 AЈ→BЈ 2 AЈ transitions to predissociative states of the exciplex by making a separable approximation in Jacobi coordinates. Theoretical simulation based on ab initio energies and transition dipole moments produced an excitation spectrum that is in good agreement with the experimental data. Including the dependence of the transition dipole moment on nuclear geometry had only a small quantitative effect on the calculated photoabsorption spectrum. The present calculation, in spite of the approximations involved, provides a semiquantitative description of the experimental spectrum of the resonance states in the funnel and allows us to explain all the main features of the spectrum.

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Photoexcitation of the NaKCl Reaction Complex

Cited by 53 publications

References 9 publications

Probing electronic rearrangement during chemical reactions

Probing electronic rearrangement during chemical reactions

Laser stimulation and observation of bimolecular reactions

The photoabsorption spectrum of Na⋯FH van der Waals molecule: Comparison of theory and experiment for a harpooning reaction studied by transition state spectroscopy

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