Potential energy surfaces of bound and metastable electron-attached states of N2O characterized by a joint experimental and theoretical study

被引：0

作者：

Mukherjee, Madhubani ^{[1
]}

Baker, Carson ^{[1
]}

Rankovic, Milos ^{[2
]}

Nag, Pamir ^{[2
]}

Fedor, Juraj ^{[2
]}

Krylov, Anna I. ^{[1
]}

机构：

[1] Univ Southern Calif, Dept Chem, Los Angeles, CA 90089 USA

[2] Czech Acad Sci, J Heyrovsky Inst Phys Chem, Dolejskova 3, Prague 8, Czech Republic

来源：

JOURNAL OF CHEMICAL PHYSICS | 2025年 / 163卷 / 02期

基金：

美国国家科学基金会;

关键词：

CROSS-SECTIONS; DISSOCIATIVE ATTACHMENT; COLLISIONAL IONIZATION; QUANTUM-CHEMISTRY; NEGATIVE-ION; OPEN-SHELL; CO2; RESONANCE; SCATTERING; AFFINITIES;

D O I：

10.1063/5.0273585

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：

We report a combined experimental and theoretical investigation of electron scattering from nitrous oxide (N2O). Experimental two-dimensional electron energy loss spectra (EELS) provide information about vibrational states of a molecule and about potential energy surfaces of anionic resonances. This study reports the EELS measured at 2.5-2.6 eV incident energy. The calculations using complex-valued extensions of equation-of-motion coupled-cluster theory (based on the non-Hermitian quantum mechanics) facilitate the assignment of all major EELS features. Our simulations identified two broad and partially overlapping resonances-one of pi* and another of sigma* character-located at similar to 2.8 and 2.3 eV vertically at the equilibrium geometry of the neutral. Due to the Renner-Teller effect, the pi* resonance splits upon bending. The upper state, (2)Pi, remains linear. The lower state mixes with the sigma* configuration, giving rise to the (2)A ' resonance, which becomes strongly stabilized at bent geometries (alpha(NNO) = 134 degrees), resulting in very low adiabatic electron attachment energy. The calculations estimate the electron affinity of N2O to be -0.140 eV. The (2)A ' state is predissociative, with the barrier for the N-O bond dissociation of 0.183 eV. The measured EELS feature sharp vibrational structures at low energy losses, followed by a linear (in logarithmic scale) tail extending to the maximum energy loss. The simulations attribute the sharp features at the low energy loss to the non-resonant excitations and contributions from the cold (2)Pi resonance. The tail is attributed to the vibrationally hot (2)A ' state, and its slope is determined by the excess energy available in this state.

引用

页数：14

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