### Abstract

The 2ν_{4} band spectrum of ^{14}NO_{3} observed with infrared diode laser spectroscopy was analyzed with the Fourier transform (FT) spectrum in the 760 cm^{−1} region, including the Coriolis interaction between v_{4} = 2 and v_{2} = 1. The vibrational frequencies of v_{4} = 2, l = 0, and l = ±2 have been determined to be 752.4033(86) and 771.7941(81) cm^{−1}, respectively. By considering the anharmonic interaction among the 2ν_{4}, ν_{3}, ν_{4}, ν_{2}, and ν_{2} + 3ν_{4} states, a relation among the cubic anharmonic constants was obtained as 0.452 Φ_{444}ζ_{2,4} − 0.271 Φ_{344}ζ_{2,3} = 127.7 cm^{−1}. The ratio of transition moments μ(ν_{2})/μ(2ν_{4}) was determined to be 0.3 from the perturbation analysis. The second strongest infrared band of ^{14}NO_{3}, ν_{3} + 2ν_{4}, observed around 1927 cm^{−1} has been analyzed with the hot band ν_{3} + 2ν_{4} − ν_{4} by including the Coriolis interaction with the v_{2} = 1, v_{4} = 3 state. Similarly, the same band of ^{15}NO_{3} was analyzed to give the band origin of 1897.9325(6) cm^{−1}. The isotope shift 28.2 cm^{−1} for the ν_{3} + 2ν_{4} vibrational frequency is consistent with a predicted value of 27.3 cm^{−1}. Although there are two A' states in v_{3} = 1, v_{4} = 2, only one A_{2}' state has been assigned in the hot band, indicating that the other band has weak intensity. This fact and the strong intensity of the ν_{3} + 2ν_{4} band (l_{3} = ±1, l_{4} = 0) are understood as the effect of vibronic interaction. The first-order Coriolis coupling constant ζ of ν_{3} + 2ν_{4}, l_{3} = 1, l_{4} = 0 is similar to those of the ν_{4} and ν_{3} + ν_{4} states, and it is concluded that the vibrational Coriolis coupling constant is nearly zero and the observed constants of ζ = −0.19 (^{14}NO_{3}) and ζ = −0.15 (^{15}NO_{3}) also originate from the effect of vibronic interaction.

Original language | English |
---|---|

Pages (from-to) | 10-21 |

Number of pages | 12 |

Journal | Journal of Molecular Spectroscopy |

Volume | 334 |

DOIs | |

Publication status | Published - Apr 1 2017 |

### Fingerprint

### Keywords

- 2ν and ν + 2ν vibration
- IR spectroscopy
- Nitrate radical
- Vibronic interaction

### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics
- Spectroscopy
- Physical and Theoretical Chemistry

### Cite this

_{4}and ν

_{3}+ 2ν

_{4}bands of the NO

_{3}radical.

*Journal of Molecular Spectroscopy*,

*334*, 10-21. https://doi.org/10.1016/j.jms.2017.02.008

**Infrared spectroscopy of 2ν _{4} and ν_{3} + 2ν_{4} bands of the NO_{3} radical.** / Kawaguchi, Kentarou; Narahara, Tatsuo; Fujimori, Ryuji; Tang, Jian; Ishiwata, Takashi.

Research output: Contribution to journal › Article

_{4}and ν

_{3}+ 2ν

_{4}bands of the NO

_{3}radical',

*Journal of Molecular Spectroscopy*, vol. 334, pp. 10-21. https://doi.org/10.1016/j.jms.2017.02.008

_{4}and ν

_{3}+ 2ν

_{4}bands of the NO

_{3}radical. Journal of Molecular Spectroscopy. 2017 Apr 1;334:10-21. https://doi.org/10.1016/j.jms.2017.02.008

}

TY - JOUR

T1 - Infrared spectroscopy of 2ν4 and ν3 + 2ν4 bands of the NO3 radical

AU - Kawaguchi, Kentarou

AU - Narahara, Tatsuo

AU - Fujimori, Ryuji

AU - Tang, Jian

AU - Ishiwata, Takashi

PY - 2017/4/1

Y1 - 2017/4/1

N2 - The 2ν4 band spectrum of 14NO3 observed with infrared diode laser spectroscopy was analyzed with the Fourier transform (FT) spectrum in the 760 cm−1 region, including the Coriolis interaction between v4 = 2 and v2 = 1. The vibrational frequencies of v4 = 2, l = 0, and l = ±2 have been determined to be 752.4033(86) and 771.7941(81) cm−1, respectively. By considering the anharmonic interaction among the 2ν4, ν3, ν4, ν2, and ν2 + 3ν4 states, a relation among the cubic anharmonic constants was obtained as 0.452 Φ444ζ2,4 − 0.271 Φ344ζ2,3 = 127.7 cm−1. The ratio of transition moments μ(ν2)/μ(2ν4) was determined to be 0.3 from the perturbation analysis. The second strongest infrared band of 14NO3, ν3 + 2ν4, observed around 1927 cm−1 has been analyzed with the hot band ν3 + 2ν4 − ν4 by including the Coriolis interaction with the v2 = 1, v4 = 3 state. Similarly, the same band of 15NO3 was analyzed to give the band origin of 1897.9325(6) cm−1. The isotope shift 28.2 cm−1 for the ν3 + 2ν4 vibrational frequency is consistent with a predicted value of 27.3 cm−1. Although there are two A' states in v3 = 1, v4 = 2, only one A2' state has been assigned in the hot band, indicating that the other band has weak intensity. This fact and the strong intensity of the ν3 + 2ν4 band (l3 = ±1, l4 = 0) are understood as the effect of vibronic interaction. The first-order Coriolis coupling constant ζ of ν3 + 2ν4, l3 = 1, l4 = 0 is similar to those of the ν4 and ν3 + ν4 states, and it is concluded that the vibrational Coriolis coupling constant is nearly zero and the observed constants of ζ = −0.19 (14NO3) and ζ = −0.15 (15NO3) also originate from the effect of vibronic interaction.

AB - The 2ν4 band spectrum of 14NO3 observed with infrared diode laser spectroscopy was analyzed with the Fourier transform (FT) spectrum in the 760 cm−1 region, including the Coriolis interaction between v4 = 2 and v2 = 1. The vibrational frequencies of v4 = 2, l = 0, and l = ±2 have been determined to be 752.4033(86) and 771.7941(81) cm−1, respectively. By considering the anharmonic interaction among the 2ν4, ν3, ν4, ν2, and ν2 + 3ν4 states, a relation among the cubic anharmonic constants was obtained as 0.452 Φ444ζ2,4 − 0.271 Φ344ζ2,3 = 127.7 cm−1. The ratio of transition moments μ(ν2)/μ(2ν4) was determined to be 0.3 from the perturbation analysis. The second strongest infrared band of 14NO3, ν3 + 2ν4, observed around 1927 cm−1 has been analyzed with the hot band ν3 + 2ν4 − ν4 by including the Coriolis interaction with the v2 = 1, v4 = 3 state. Similarly, the same band of 15NO3 was analyzed to give the band origin of 1897.9325(6) cm−1. The isotope shift 28.2 cm−1 for the ν3 + 2ν4 vibrational frequency is consistent with a predicted value of 27.3 cm−1. Although there are two A' states in v3 = 1, v4 = 2, only one A2' state has been assigned in the hot band, indicating that the other band has weak intensity. This fact and the strong intensity of the ν3 + 2ν4 band (l3 = ±1, l4 = 0) are understood as the effect of vibronic interaction. The first-order Coriolis coupling constant ζ of ν3 + 2ν4, l3 = 1, l4 = 0 is similar to those of the ν4 and ν3 + ν4 states, and it is concluded that the vibrational Coriolis coupling constant is nearly zero and the observed constants of ζ = −0.19 (14NO3) and ζ = −0.15 (15NO3) also originate from the effect of vibronic interaction.

KW - 2ν and ν + 2ν vibration

KW - IR spectroscopy

KW - Nitrate radical

KW - Vibronic interaction

UR - http://www.scopus.com/inward/record.url?scp=85015657590&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85015657590&partnerID=8YFLogxK

U2 - 10.1016/j.jms.2017.02.008

DO - 10.1016/j.jms.2017.02.008

M3 - Article

AN - SCOPUS:85015657590

VL - 334

SP - 10

EP - 21

JO - Journal of Molecular Spectroscopy

JF - Journal of Molecular Spectroscopy

SN - 0022-2852

ER -