Ortho-para mixing hyperfine interaction in the H2O+ ion and nuclear spin equilibration

Keiichi Tanaka, Kensuke Harada, Takeshi Oka

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

The ortho to para conversion of water ion, H2O+, due to the interaction between the magnetic moments of the unpaired electron and protons has been theoretically studied to calculate the spontaneous emission lifetime between the ortho- and para-levels. The electron spin-nuclear spin interaction term, Tab(SaΔIb + S bΔIa) mixes ortho (I = 1) and para (I = 0) levels to cause the "forbidden" ortho to para |ΔI| = 1 transition. The mixing term with Tab = 72.0 MHz is 4 orders of magnitude higher for H2O+ than for its neutral counterpart H2O where the magnetic field interacting with proton spins is by molecular rotation rather than the free electron. The resultant 108 increase of ortho to para conversion rate possibly makes the effect of conversion in H 2O+ measurable in laboratories and possibly explains the anomalous ortho to para ratio recently reported by Herschel heterodyne instrument for the far-infrared (HIFI) observation. Results of our calculations show that the ortho ↔ para mixings involving near-degenerate ortho and para levels are high (∼10-3), but they tend to occur at high energy levels, ∼300 K. Because of the rapid spontaneous emission, such high levels are not populated in diffuse clouds unless the radiative temperature of the environment is very high. The low-lying 101 (para) and 111 (ortho) levels of H2O+ are mixed by ∼10-4 making the spontaneous emission lifetime for the para 101 → ortho 000 transition 520 years and 5200 years depending on the F value of the hyperfine structure. Thus the ortho ↔ para conversion due to the unpaired electron is not likely to seriously affect thermalization of interstellar H2O+ unless either the radiative temperature is very high or number density of the cloud is very low.

Original languageEnglish
Pages (from-to)9584-9592
Number of pages9
JournalJournal of Physical Chemistry A
Volume117
Issue number39
DOIs
Publication statusPublished - Oct 3 2013

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nuclear spin
Spontaneous emission
Ions
Electrons
spontaneous emission
Protons
ions
interactions
ortho para conversion
life (durability)
Magnetic moments
molecular rotation
protons
Electron energy levels
hyperfine structure
electron spin
free electrons
Magnetic fields
Infrared radiation
electrons

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Ortho-para mixing hyperfine interaction in the H2O+ ion and nuclear spin equilibration. / Tanaka, Keiichi; Harada, Kensuke; Oka, Takeshi.

In: Journal of Physical Chemistry A, Vol. 117, No. 39, 03.10.2013, p. 9584-9592.

Research output: Contribution to journalArticle

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N2 - The ortho to para conversion of water ion, H2O+, due to the interaction between the magnetic moments of the unpaired electron and protons has been theoretically studied to calculate the spontaneous emission lifetime between the ortho- and para-levels. The electron spin-nuclear spin interaction term, Tab(SaΔIb + S bΔIa) mixes ortho (I = 1) and para (I = 0) levels to cause the "forbidden" ortho to para |ΔI| = 1 transition. The mixing term with Tab = 72.0 MHz is 4 orders of magnitude higher for H2O+ than for its neutral counterpart H2O where the magnetic field interacting with proton spins is by molecular rotation rather than the free electron. The resultant 108 increase of ortho to para conversion rate possibly makes the effect of conversion in H 2O+ measurable in laboratories and possibly explains the anomalous ortho to para ratio recently reported by Herschel heterodyne instrument for the far-infrared (HIFI) observation. Results of our calculations show that the ortho ↔ para mixings involving near-degenerate ortho and para levels are high (∼10-3), but they tend to occur at high energy levels, ∼300 K. Because of the rapid spontaneous emission, such high levels are not populated in diffuse clouds unless the radiative temperature of the environment is very high. The low-lying 101 (para) and 111 (ortho) levels of H2O+ are mixed by ∼10-4 making the spontaneous emission lifetime for the para 101 → ortho 000 transition 520 years and 5200 years depending on the F value of the hyperfine structure. Thus the ortho ↔ para conversion due to the unpaired electron is not likely to seriously affect thermalization of interstellar H2O+ unless either the radiative temperature is very high or number density of the cloud is very low.

AB - The ortho to para conversion of water ion, H2O+, due to the interaction between the magnetic moments of the unpaired electron and protons has been theoretically studied to calculate the spontaneous emission lifetime between the ortho- and para-levels. The electron spin-nuclear spin interaction term, Tab(SaΔIb + S bΔIa) mixes ortho (I = 1) and para (I = 0) levels to cause the "forbidden" ortho to para |ΔI| = 1 transition. The mixing term with Tab = 72.0 MHz is 4 orders of magnitude higher for H2O+ than for its neutral counterpart H2O where the magnetic field interacting with proton spins is by molecular rotation rather than the free electron. The resultant 108 increase of ortho to para conversion rate possibly makes the effect of conversion in H 2O+ measurable in laboratories and possibly explains the anomalous ortho to para ratio recently reported by Herschel heterodyne instrument for the far-infrared (HIFI) observation. Results of our calculations show that the ortho ↔ para mixings involving near-degenerate ortho and para levels are high (∼10-3), but they tend to occur at high energy levels, ∼300 K. Because of the rapid spontaneous emission, such high levels are not populated in diffuse clouds unless the radiative temperature of the environment is very high. The low-lying 101 (para) and 111 (ortho) levels of H2O+ are mixed by ∼10-4 making the spontaneous emission lifetime for the para 101 → ortho 000 transition 520 years and 5200 years depending on the F value of the hyperfine structure. Thus the ortho ↔ para conversion due to the unpaired electron is not likely to seriously affect thermalization of interstellar H2O+ unless either the radiative temperature is very high or number density of the cloud is very low.

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