Rotational transitions of the nonlinear triatomic molecular anion NH_{2}^{-} have been observed by terahertz spectroscopy in a cryogenic radio frequency ion trap. Absorption of terahertz photons has been probed by rotational state-dependent photodetachment of the trapped negative ions near the detachment threshold. Using this two-photon scheme, the two lowest rotational transitions for the asymmetric top rotor NH_{2}^{-} have been found. For the para nuclear spin configuration, the 1_{0}←0_{0} transition frequency was determined to be 933 954(2) MHz, and for the ortho configuration the 1_{+1}←1_{-1} transition frequency was determined to be 447 375(3) MHz. This result appears to preclude the recent tentative assignment of an interstellar absorption feature to NH_{2}^{-}.
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http://dx.doi.org/10.1103/PhysRevLett.120.253003 | DOI Listing |
Phys Chem Chem Phys
January 2025
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577, Japan.
We present a general theory of quantum chemistry-based atomic momentum spectroscopy (QC-AMS) for predicting electron-atom Compton profiles due to the intramolecular motion of each atom in diatomic, triatomic and polyatomic molecules. The atomic motion is assumed to be decomposable into normal-mode molecular vibrations and molecular rotations, and the latter are treated classically. An accuracy assessment of the general theory is performed through comparisons with the AMS Compton profiles of HD and NO, predicted by the full quantum chemistry-based AMS theory that is precise but can work only for diatomic molecules.
View Article and Find Full Text PDFJ Chem Theory Comput
January 2025
Department of Chemistry, University of Warwick, Coventry CV4 7AL, U.K.
Inductive program synthesis (PS) has recently begun to emerge as a useful new approach to automatically generate algorithms in quantum chemistry, as demonstrated in recent applications to the vibrational Schrödinger equation for simple model systems with one or two degrees-of-freedom. Here, we report a new physics-informed approach to inductive PS that is more conducive to the generation of discrete variable representation algorithms for real molecular systems. The new framework ensures separability of the kinetic and potential operators and does not require an exact solution to compare synthesized algorithmic predictions with.
View Article and Find Full Text PDFJ Phys Chem Lett
December 2024
Raymond and Beverly Sackler Faculty of Exact Sciences, School of Chemistry, Tel Aviv University, Tel Aviv 6997801, Israel.
The "l-Doubling" phenomenon emanates from the coupling between molecular rotations and perpendicular vibrations (bending modes) in polyatomic molecules. This elusive phenomenon has been largely discarded in laser-induced molecular alignment. Here we explore and unveil the ramifications of l-Doubling on the coherent rotational dynamics of linear triatomic molecules at ambient temperatures and above.
View Article and Find Full Text PDFMolecules
August 2024
Institute of Fundamental Physics (IFF-CSIC), CSIC, Serrano 123, 28006 Madrid, Spain.
We present a computational investigation on the structural arrangements and energetic stabilities of small-size protonated argon clusters, Ar nH +. Using high-level ab initio electronic structure computations, we determined that the linear symmetric triatomic ArH +Ar ion serves as the molecular core for all larger clusters studied. Through harmonic normal-mode analysis for clusters containing up to seven argon atoms, we observed that the proton-shared vibration shifts to lower frequencies, consistent with measurements in gas-phase IRPD and solid Ar-matrix isolation experiments.
View Article and Find Full Text PDFJ Phys Chem A
September 2024
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
The interaction-asymptotic region decomposition (IARD) technique has been proven to be a good solution to the long-standing coordinate problem in reactive scattering calculations. In this work, the IARD technique was further developed using Jacobi coordinates for the interaction region, instead of the previously used hyperspherical coordinates. Although the Jacobi coordinate may not be as optimal as the hyperspherical coordinates for describing the interaction region in reactive scattering processes, it has simpler kinetic operators and provides a more physically intuitive picture.
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