A kinetic stability study of MN5 (M=Li, Na, K, and Rb)

Jun Fang Zhao; Nan Li; Qian Shu Li

doi:10.1007/s00214-003-0440-8

A kinetic stability study of MN₅ (M=Li, Na, K, and Rb)

Jun Fang Zhao, Nan Li, Qian Shu Li^*

^*Corresponding author for this work

School of Mechatronical Engineering

Beijing Institute of Technology

Research output: Contribution to journal › Article › peer-review

31 Citations (Scopus)

Abstract

A structure and kinetic stability study on some complexes with the general formula MN₅, where M are the alkali-metal atoms, Li, Na, K, and Rb, has been carried by using hybrid density functional methods. Complex B (C _2v) with two points of attachment to the N₅ ring is the most energetically favored for all metals considered here. Pyramidal structures A (C_5v) are kinetically unstable and they rapidly rearrange to the most stable planar structures B. At the QCISD(T)/6-311 + G*//B3LYP/6-311 + G* + ZPE (B3LYP/6-311 + G*) level, the decomposition barrier heights of LiN₅-B, NaN₅-B, KN₅-B, and RbN ₅-B are predicted to be 19.9, 22.0, 22.5, and 23.0 kcal/mol, respectively. In addition, the rate constants of the decomposition reaction MN₅-B → MN₃ + N₂ (M=Li, Na, K, and Rb) are also predicted using conventional transition state theory and canonical variational transition state theory, respectively.

Original language	English
Pages (from-to)	10-18
Number of pages	9
Journal	Theoretical Chemistry Accounts
Volume	110
Issue number	1
DOIs	https://doi.org/10.1007/s00214-003-0440-8
Publication status	Published - 1 Aug 2003

Keywords

Density functional theory calculations
Kinetic stability
MN complex

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title = "A kinetic stability study of MN5 (M=Li, Na, K, and Rb)",

abstract = "A structure and kinetic stability study on some complexes with the general formula MN5, where M are the alkali-metal atoms, Li, Na, K, and Rb, has been carried by using hybrid density functional methods. Complex B (C 2v) with two points of attachment to the N5 ring is the most energetically favored for all metals considered here. Pyramidal structures A (C5v) are kinetically unstable and they rapidly rearrange to the most stable planar structures B. At the QCISD(T)/6-311 + G*//B3LYP/6-311 + G* + ZPE (B3LYP/6-311 + G*) level, the decomposition barrier heights of LiN5-B, NaN5-B, KN5-B, and RbN 5-B are predicted to be 19.9, 22.0, 22.5, and 23.0 kcal/mol, respectively. In addition, the rate constants of the decomposition reaction MN5-B → MN3 + N2 (M=Li, Na, K, and Rb) are also predicted using conventional transition state theory and canonical variational transition state theory, respectively.",

keywords = "Density functional theory calculations, Kinetic stability, MN complex",

author = "Zhao, \{Jun Fang\} and Nan Li and Li, \{Qian Shu\}",

year = "2003",

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doi = "10.1007/s00214-003-0440-8",

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T1 - A kinetic stability study of MN5 (M=Li, Na, K, and Rb)

AU - Zhao, Jun Fang

AU - Li, Nan

AU - Li, Qian Shu

PY - 2003/8/1

Y1 - 2003/8/1

N2 - A structure and kinetic stability study on some complexes with the general formula MN5, where M are the alkali-metal atoms, Li, Na, K, and Rb, has been carried by using hybrid density functional methods. Complex B (C 2v) with two points of attachment to the N5 ring is the most energetically favored for all metals considered here. Pyramidal structures A (C5v) are kinetically unstable and they rapidly rearrange to the most stable planar structures B. At the QCISD(T)/6-311 + G*//B3LYP/6-311 + G* + ZPE (B3LYP/6-311 + G*) level, the decomposition barrier heights of LiN5-B, NaN5-B, KN5-B, and RbN 5-B are predicted to be 19.9, 22.0, 22.5, and 23.0 kcal/mol, respectively. In addition, the rate constants of the decomposition reaction MN5-B → MN3 + N2 (M=Li, Na, K, and Rb) are also predicted using conventional transition state theory and canonical variational transition state theory, respectively.

AB - A structure and kinetic stability study on some complexes with the general formula MN5, where M are the alkali-metal atoms, Li, Na, K, and Rb, has been carried by using hybrid density functional methods. Complex B (C 2v) with two points of attachment to the N5 ring is the most energetically favored for all metals considered here. Pyramidal structures A (C5v) are kinetically unstable and they rapidly rearrange to the most stable planar structures B. At the QCISD(T)/6-311 + G*//B3LYP/6-311 + G* + ZPE (B3LYP/6-311 + G*) level, the decomposition barrier heights of LiN5-B, NaN5-B, KN5-B, and RbN 5-B are predicted to be 19.9, 22.0, 22.5, and 23.0 kcal/mol, respectively. In addition, the rate constants of the decomposition reaction MN5-B → MN3 + N2 (M=Li, Na, K, and Rb) are also predicted using conventional transition state theory and canonical variational transition state theory, respectively.

KW - Density functional theory calculations

KW - Kinetic stability

KW - MN complex

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DO - 10.1007/s00214-003-0440-8

M3 - Article

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SN - 1432-881X

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EP - 18

JO - Theoretical Chemistry Accounts

JF - Theoretical Chemistry Accounts

IS - 1

ER -

A kinetic stability study of MN₅ (M=Li, Na, K, and Rb)

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Keywords

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