Electronic Signatures of Large Amplitude Motions:  Dipole Moments of Vibrationally Excited Local-Bend and Local-Stretch States of S0Acetylene†

2006 ◽  
Vol 110 (38) ◽  
pp. 18912-18920 ◽  
Author(s):  
Bryan M. Wong ◽  
Adam H. Steeves ◽  
Robert W. Field
Keyword(s):  
Large Amplitude ◽  
Dipole Moments ◽  
Vibrationally Excited ◽  
Electronic Signatures ◽  
Large Amplitude Motions

The Relative Orientation of the Total Dipole Moment in the N-cis Lone-Electron-Pair-Trans Isomer of Allylamine

1980 ◽  
Vol 35 (4) ◽  
pp. 415-417 ◽  
Author(s):  
Edmund Fischer ◽  
Ivan Botskor
Keyword(s):  
Dipole Moment ◽  
Trans Isomer ◽  
Large Amplitude ◽  
Lone Electron Pair ◽  
Electron Pair ◽  
Dipole Moments ◽  
Relative Orientation ◽  
Total Dipole Moment ◽  
Principal Axes ◽  
Large Amplitude Motions

Abstract The dipole moment of the doubly deuterated species (CH2=CH-CH2-ND2) of N-cis Lone-electron-pair isomer of allylamine has been measured. The "isotope pulling elfect" has been used to determine the relative orientation of the total dipole moment with respect to the principal axes in the normal species. The possible effects of large amplitude motions on the observed effective dipole moments are discussed.

scholarly journals Understanding (coupled) large amplitude motions: the interplay of microwave spectroscopy, spectral modeling, and quantum chemistry

2020 ◽  
Vol 0 (0) ◽  
Author(s):  
Ha Vinh Lam Nguyen ◽  
Isabelle Kleiner
Keyword(s):  
Fourier Transform ◽  
Quantum Chemistry ◽  
Large Amplitude ◽  
Environmental Chemistry ◽  
Broad Band ◽  
Microwave Spectroscopy ◽  
Rotational Spectrum ◽  
Spectral Modeling ◽  
Rotational Spectra ◽  
Large Amplitude Motions

AbstractA large variety of molecules contain large amplitude motions (LAMs), inter alia internal rotation and inversion tunneling, resulting in tunneling splittings in their rotational spectrum. We will present the modern strategy to study LAMs using a combination of molecular jet Fourier transform microwave spectroscopy, spectral modeling, and quantum chemical calculations to characterize such systems by the analysis of their rotational spectra. This interplay is particularly successful in decoding complex spectra revealing LAMs and providing reference data for fundamental physics, astrochemistry, atmospheric/environmental chemistry and analytics, or fundamental researches in physical chemistry. Addressing experimental key aspects, a brief presentation on the two most popular types of state-of-the-art Fourier transform microwave spectrometer technology, i.e., pulsed supersonic jet expansion–based spectrometers employing narrow-band pulse or broad-band chirp excitation, will be given first. Secondly, the use of quantum chemistry as a supporting tool for rotational spectroscopy will be discussed with emphasis on conformational analysis. Several computer codes for fitting rotational spectra exhibiting fine structure arising from LAMs are discussed with their advantages and drawbacks. Furthermore, a number of examples will provide an overview on the wealth of information that can be drawn from the rotational spectra, leading to new insights into the molecular structure and dynamics. The focus will be on the interpretation of potential barriers and how LAMs can act as sensors within molecules to help us understand the molecular behavior in the laboratory and nature.

Dipole Moments of Highly Vibrationally Excited Water

Science ◽  
2002 ◽  
Vol 297 (5583) ◽  
pp. 993-995 ◽  
Author(s):  
A. Callegari
Keyword(s):  
Dipole Moments ◽  
Vibrationally Excited

Generalized Modes in Time-Domain Seakeeping Calculations

2012 ◽  
Vol 56 (04) ◽  
pp. 215-233
Author(s):  
Johan T. Tuitman ◽  
Šime Malenica ◽  
Riaan van't Veer
Keyword(s):  
Rigid Body ◽  
Transient Response ◽  
Time Domain ◽  
Large Amplitude ◽  
Degrees Of Freedom ◽  
Mode Shapes ◽  
Nonlinear Load ◽  
Large Amplitude Motions ◽  
Rigid Body Modes ◽  
The Time Domain

The concept of "generalized modes" is to describe all degrees of freedom by mode shapes and not using any predefined shape, like rigid body modes. Generalized modes in seakeeping computations allow one to calculate the response of a single ship, springing, whipping, multibody interaction, etc., using a uniform approach. The generalized modes have already been used for frequency-domain seakeeping calculations by various authors. This article extents the generalized modes methodology to be used for time-domain seakeeping computations, which accounts for large-amplitude motions of the rigid-body modes. The time domain can be desirable for seakeeping computations because it is easy to include nonlinear load components and to compute transient response, like slamming and whipping. Results of multibody interaction, two barges connected by a hinge, whipping response of a ferry resulting from slamming loads, and the response of a flexible barge are presented to illustrate the theory.

Preferred Rotameric Conformations of Isobutyraldehyde, Their Dipole Moments and Vibrationally Excited States by Microwave Spectroscopy

1986 ◽  
Vol 41 (3) ◽  
pp. 483-490 ◽  
Author(s):  
O. L. Stiefvater
Keyword(s):  
Oxygen Atom ◽  
Excited States ◽  
Ground State ◽  
Dipole Moments ◽  
Microwave Spectroscopy ◽  
Centrifugal Distortion ◽  
Gauche Conformation ◽  
Vibrationally Excited ◽  
Trans Conformation ◽  
Centrifugal Distortion Constants

The earlier prediction of the preferred and the less stable rotameric conformations of isobutyraldehyde, (CH3)2CHCHO, has been confirmed experimentally by microwave spectroscopy. The compound exists mainly in a gauche conformation, in which one of the methyl groups is eclipsed by the oxygen atom, and the less stable rotamer is the trans conformation, in which the oxygen atom eclipses the isopropyl hydrogen.Ground state rotational constants (in MHz) and centrifugal distortion constants (in kHz), together with dipole moments (in D), are:Rotation spectra due to three torsionally excited states of each rotamer have been identified, along with satellites arising from CH3 internal rotation and CC2 wagging.

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