Electronic Quenching of N(2D) by N2: Theoretical Predictions, Comparison with Experimental Rate Constants, and Impact on Atmospheric Modeling

被引：25

作者：

Galvao, B. R. L. ^{[1
]}

Varandas, A. J. C. ^{[2
,3
]}

Braga, J. P. ^{[1
]}

Belchior, J. C. ^{[1
]}

机构：

[1] Univ Fed Minas Gerais, Dept Quim ICEx, BR-31270901 Belo Horizonte, MG, Brazil

[2] Univ Coimbra, Dept Quim, P-3004535 Coimbra, Portugal

[3] Univ Coimbra, Ctr Quim, P-3004535 Coimbra, Portugal

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2013年 / 4卷 / 14期

关键词：

EXCITED NITROGEN-ATOMS; AB-INITIO; EXCHANGE-REACTION; SURFACE; DEACTIVATION; MOLECULES; QUANTUM; DISSOCIATION; PHOTOLYSIS; COLLISIONS;

D O I：

10.1021/jz401012t

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Rate constants for the electronic quenching reaction N(D-2) + N-2 -> N(S-4) + N-2 are calculated for temperatures over the range of 240 <= T/K <= 1000 using an accurate set of three global electronic potential energy surfaces for the N-3 system ((4)A '', (2)A', and (2)A ''). The nuclear motion is treated by running quasiclassical trajectories, incorporating spin-forbidden transitions with the trajectory surface hopping method. The exclusively theoretical results are compared with available experimental data for the reaction and contribute to clarify the discrepancies among them. The rate constants at higher temperatures achieved in the atmosphere, for which no experiments have been performed, are presented for the first time. The impact of the results in atmospheric modeling is analyzed, predicting at what altitudes this reaction will play an important role.

引用

页码：2292 / 2297

页数：6

共 42 条

[1] [Anonymous], 2009, CAMBRIDGE ATMOSPHERI
[2] VACUUM-ULTRAVIOLET PHOTOLYSIS OF N2O. .4. DEACTIVATION OF N(2D)
BLACK, G
SLANGER, TG
STJOHN, GA
YOUNG, RA
[J]. JOURNAL OF CHEMICAL PHYSICS, 1969, 51 (01) : 116 - &
[3] Quasiclassical Trajectory Study of Atom-Exchange and Vibrational Relaxation Processes in Collisions of Atomic and Molecular Nitrogen
Caridade, P. J. S. B.
Galvao, B. R. L.
Varandas, A. J. C.
[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2010, 114 (19) : 6063 - 6070
[4] QUENCHING OF N(2D) BY O(3P)
DAVENPORT, JE
SLANGER, TG
BLACK, G
[J]. JOURNAL OF GEOPHYSICAL RESEARCH-SPACE PHYSICS, 1976, 81 (01): : 12 - 16
[5] Quasiclassical trajectory study of NO vibrational relaxation by collisions with atomic oxygen
Duff, JW
Sharma, RD
[J]. JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1997, 93 (16): : 2645 - 2649
[6] Quasi-classical dynamics and vibrational kinetics of N+N2(ν) system
Esposito, F
Capitelli, M
Gorse, C
[J]. CHEMICAL PHYSICS, 2000, 257 (2-3) : 193 - 202
[7] RAPID DEACTIVATION OF N(2D) BY O - IMPACT ON THERMOSPHERIC AND MESOSPHERIC ODD NITROGEN
FESEN, CG
GERARD, JC
RUSCH, DW
[J]. JOURNAL OF GEOPHYSICAL RESEARCH-SPACE PHYSICS, 1989, 94 (A5): : 5419 - 5426
[8] N(4S/2D)+N2: Accurate ab initio-based DMBE potential energy surfaces and surface-hopping dynamics
Galvao, B. R. L.
Caridade, P. J. S. B.
Varandas, A. J. C.
[J]. JOURNAL OF CHEMICAL PHYSICS, 2012, 137 (22)
[9] Ab Initio Based Double-Sheeted DMBE Potential Energy Surface for N3(2A") and Exploratory Dynamics Calculations
Galvao, B. R. L.
Varandas, A. J. C.
[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2011, 115 (44) : 12390 - 12398
[10] Accurate Double Many-Body Expansion Potential Energy Surface for N3(4A") from Correlation Scaled ab Initio Energies with Extrapolation to the Complete Basis Set Limit
Galvao, B. R. L.
Varandas, A. J. C.
[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2009, 113 (52) : 14424 - 14430

← 1 2 3 4 5 →