A reinterpretation of the unusual barochromism of azulene

2007 ◽  
Vol 85 (6) ◽  
pp. 432-437 ◽  
Author(s):  
Masami Okamoto ◽  
Satoshi Hirayama ◽  
Ronald P Steer
Keyword(s):  
Excited States ◽  
Room Temperature ◽  
Dipole Moments ◽  
Applied Pressure ◽  
Electronic States ◽  
Acetonitrile Solution ◽  
Analytical Relationship ◽  
Hypsochromic Shift ◽  
Absorption Bands ◽  
Solvatochromic Shifts

The UV–vis spectra of azulene in methylcyclohexane and acetonitrile solution at room temperature have been measured as a function of applied pressure in the 0.1–600 MPa range. The solvatochromic shifts are normal, but the barochromic shifts are unusual (hypsochromic shift in the S1–S0 absorption bands vs. normal bathochromic shifts in its S2–S0 and S3–S0 absorption bands). An analytical relationship between the barochromic shift and the differences in the polarizabilities and dipole moments of the two radiatively coupled electronic states has been derived. The unusual barochromism of azulene has been reinterpreted in terms of differences in the polarizabilities of azulene in its ground and excited states and the dominance of dispersive interactions in barochromism.Key words: barochromism, solvatochromism, azulene, polarizability, dipole moment.

On excited states of the Au3 cluster: an ab initio study

Open Physics ◽  
2008 ◽  
Vol 6 (4) ◽  
Author(s):  
Alexander Rusakov ◽  
André Zaitsevskii
Keyword(s):  
Excited States ◽  
Spectroscopic Data ◽  
Reasonable Agreement ◽  
Dipole Moments ◽  
Electronic States ◽  
Ab Initio Study ◽  
Many Body ◽  
Transition Energies ◽  
Vertical Transition ◽  
Theoretical Results

AbstractExcited electronic states of the Au3 cluster are studied within the shape-consistent small-core relativistic pseudopotential model using many-body multipartitioning perturbation theory. Vertical transition energies and dipole moments are evaluated. For highly symmetric isomer, these theoretical results are in reasonable agreement with spectroscopic data from experiments.

Visible Luminescence of Eu3+ Ions in Lithium Barium Borate Glass

2016 ◽  
Vol 702 ◽  
pp. 66-70
Author(s):  
Keerati Kirdsiri ◽  
Benchaphorn Damdee ◽  
Jakrapong Kaewkhao
Keyword(s):  
Excited States ◽  
Ground State ◽  
Room Temperature ◽  
State Level ◽  
Barium Borate ◽  
Absorption Bands ◽  
Visible Luminescence ◽  
Barium Borate Glass ◽  
Quench Method ◽  
Ground State Level

Europium doped lithium barium borate glasses were fabricated by conventional melt-quench method and were analyzed their physical, optical and luminescence properties through absorption, excitation, emission and decay analysis at room temperature. The experimental data revealed that the five discrete absorption bands peaking at 393, 464, 532, 2032 and 2212 nm due to the transitions from 7F0 ground state level to various excited states of Eu3+ ions. The luminescence of Eu3+ in visible bands were observed under 394 nm pumping.

The absorption spectrum of gaseous hydrogen bromide in the Schumann region - II. Electronic states

1961 ◽  
Vol 263 (1313) ◽  
pp. 277-288 ◽  
Keyword(s):  
Absorption Spectrum ◽  
Excited States ◽  
Hydrogen Bromide ◽  
Electronic States ◽  
Orbit Interaction ◽  
Gaseous Hydrogen ◽  
Spin Orbit ◽  
Absorption Bands ◽  
Atomic Orbitals ◽  
Region Ii

The electronic states of HBr are discussed. The large number of states observed in the region 8·2 to 10·4 eV (part I) arise by the addition of an electron to the HBr + ( X 2 II i ) core. These are ‘highly excited’ states in which molecular orbitals derived from excited atomic orbitals are occupied. Coupling cases similar to those shown in the highly excited states of H 2 and of He 2 are envisaged, but the situation in HBr is complicated by the orbital angular momentum of the HBr + ion and by spin-orbit interaction. It is suggested that these coupling cases give rise to the unusual rotational structures observed in some of the absorption bands.

Solvatochromism Effects on the Photo-Physical Behavior of Two Triazole Compounds

2016 ◽  
Vol 230 (11) ◽  
Author(s):  
Roshanak Kian ◽  
Seyed  Masoud Seyed Ahmadian ◽  
Mohammad  Sadegh Zakerhamidi ◽  
Ghader Babaie ◽  
Parviz Nesari
Keyword(s):  
Excited States ◽  
Room Temperature ◽  
Dipole Moments ◽  
Triazole Ring ◽  
Biological Applications ◽  
Physical Behavior ◽  
Energy Relationships ◽  
Linear Solvation Energy ◽  
Solute Interactions ◽  
Molecular Skeleton

AbstractDiverse biological applications of triazole molecules, makes study of these compounds intriguing. Since, the solvent effect causes different behavior in these compounds, a quantitative study of solvent effects on photo-physical properties of two triazole compounds, with similar molecular skeleton and various substituent groups on triazole ring were studied, at room temperature. The solute's photo-physical behavior strongly depends on the solute and solvent's nature, along with the solvent-solute interactions. In order to understand the effect of intermolecular interactions on spectral behaviors of these materials, and to conceive the nature and extend of solvent-solute interactions, the spectral variations were analyzed via the linear solvation energy relationships concept, suggested by Kamlet and Taft. In addition, by means of solvatochromic method, ground and excited states dipole moments as well as dipole moment variations, from ground to excited states, were calculated, in different media.

Frequency dependence of the Kerr constant

1962 ◽  
Vol 267 (1329) ◽  
pp. 271-282 ◽  
Keyword(s):  
Frequency Dependence ◽  
Excited States ◽  
Strong Electric Field ◽  
Dipole Moments ◽  
Rate Of Change ◽  
Kerr Constant ◽  
Absorption Bands ◽  
Double Beam ◽  
Solutions Of Electrolytes ◽  
The Difference

The theory of the Kerr effect is developed for wavelengths close to those corresponding to absorption bands. Unlike the transparent regions, where orientation of anisotropic molecules is the major contributor to the Kerr constant, in absorption bands distortion of the molecular structure by the strong electric field is apparently the dominant effect. For molecules with dipole moments in either the ground or the relevant excited states, the sign of the rate of change of the Kerr constant with frequency is determined by the direction of the transition moment with respect to molecular axes, and its magnitude is proportional to the square of the difference between the dipole moments of the ground and excited states. Anomalous dispersion should also occur at frequencies corresponding to forbidden transitions from the ground state, provided there is a third state with dipole transition moments with the ground and excited states. The quantum theory of the Kerr constant of gases is developed and applied to the vibration-rotation spectral region of diatomic and symmetric top molecules. A brief discussion of the potentialities of the effect is presented; since orientation is unimportant, aqueous solutions of electrolytes could presumably be studied after freezing to reduce their conductivity. An experimental method of measuring the frequency dependence of the Kerr constant, using a double beam spectrometer, is proposed.

Ground and Excited State Dipole Moments of BADAN and ACRYLODAN Determined from Solvatochromic Shifts of Absorption and Fluorescence Spectra

2001 ◽  
Vol 56 (5) ◽  
pp. 407-411 ◽  
Author(s):  
A. Kawski ◽  
B. Kukliriski ◽  
P. Bojarski
Keyword(s):  
Excited State ◽  
Excited States ◽  
Fluorescent Probes ◽  
Electric Dipole ◽  
Fluorescence Spectra ◽  
Dipole Moments ◽  
Absorption And Fluorescence Spectra ◽  
Electric Dipole Moments ◽  
Solvatochromic Shifts ◽  
Excited State Dipole Moments

Abstract The electric dipole moments in the ground μg, and excited states μe of the fluorescent probes BADAN (6-bromoacetyl-2-dimethylamino-naphthalene) and ACRYLODAN (6-acrylolyl-2-dimethylamino-naphthalene) are determined from the solvatochromic shifts of their absorption and fluorescence spec­tra for two Onsager interaction radii (a = 4.2 and 4.6 Å). The obtained values of μg and μe for BADAN are comparable to those of PRODAN, while for ACRYLODAN they are distinctly greater.

Potential energy curves and dipole moment of NF molecule with inner electron correlation

2015 ◽  
Vol 93 (12) ◽  
pp. 1544-1550 ◽  
Author(s):  
Mingjie Wan ◽  
Huafeng Luo ◽  
Chengguo Jin ◽  
Duohui Huang ◽  
Fanhou Wang
Keyword(s):  
Potential Energy ◽  
Excited States ◽  
Correlation Energy ◽  
Dipole Moments ◽  
Electronic States ◽  
Spectroscopic Properties ◽  
Potential Energy Curves ◽  
Basis Set ◽  
Triplet States ◽  
Singlet And Triplet States

The potential energy curves and dipole moments for the low-lying electronic states of the NF molecule are found by using highly accurate multireference configuration interaction plus the Davidson correction with the AV5Z basis set. All 16 electrons are used in the correlation energy calculations, which are used to characterize the spectroscopic properties of a manifold for singlet and triplet states. X3Σ–, a1Δ, b1Σ+, A3Π, 23Σ–, 23Π, 21Δ, 33Σ–, 13Σ+, and 13Δ electronic states correlate with the two lowest dissociation channels N(4Su) + F(2Pu) and N(2Du) + F(2Pu) are investigated. Note that the b1Σ+ state has two depth wells, but only one depth well was observed in the experiment. The spectroscopic parameters (Re, ωe, ωeχe, De, Be, and Te) are derived, which are in excellent agreement with the available experimental data and the other theoretical values. The molecular parameters and dipole moments for the ground and excited states are also obtained.

Crystal structure and spectral considerations of 5-methyl-2-nitraminopyridine N-oxide

2002 ◽  
Vol 80 (9) ◽  
pp. 1242-1251 ◽  
Author(s):  
A Szemik-Hojniak ◽  
T Glowiak ◽  
I Deperasinska ◽  
A Puszko
Keyword(s):  
Crystal Structure ◽  
Electronic Absorption Spectra ◽  
Dipole Moments ◽  
Oscillator Strengths ◽  
Acetonitrile Solution ◽  
Absorption Bands ◽  
Intermolecular Hydrogen Bonds ◽  
Relative Arrangement ◽  
Ci Calculations ◽  
Experimental Absorption

The crystal structure of 5-methyl-2-nitraminopyridine N-oxide (5M) has been determined and its electronic absorption spectra in the solution have been investigated. In the solid, two monomeric proton-transferred (PT) units of 5M are perpendicularly located in the crystal lattice. They are connected by two intermolecular hydrogen bonds of different strength (O-H···N 2.647(3) and 2.695(3) Å). In the gas phase the same relative arrangement of both 5M (PT) monomers has been found. As results from semiempirical PM3-CI calculations (12–14), the prototropic amino (H) [Formula: see text] imino (PT) equilibrium may occur in the solution. Assignment of experimental absorption bands to the calculated transition energies of both forms of 5M reveals that hydrogen bonded 5M (PT) dimers are dominant in cyclohexane while imino (PT) monomers seem to prevail in acetonitrile solution. The different character of electronic transitions and different relative arrangement of both monomers in amino (H) than in imino (PT) dimers are responsible for very low oscillator strengths and dipole moments of the former.Key words: crystal structure, methylated nitraminopyridine N-oxides, semiempirical PM3-CI computations, intermolecular hydrogen bonding.

THE STUDY OF THE PROPERTIES OF THE GROUND- AND LOW-LYING EXCITED STATES OF ASH2, ${\rm ASH}_{2}^{+}$ AND ${\rm ASH}_{2}^{-}$

2013 ◽  
Vol 12 (02) ◽  
pp. 1250115 ◽  
Author(s):  
YANLI HUO ◽  
MEISHAN WANG ◽  
CHUANLU YANG ◽  
HONGFEI WANG ◽  
ZIXIA MA
Keyword(s):  
Excited States ◽  
Dipole Moments ◽  
Electronic States ◽  
Theoretical Data ◽  
Ionization Potentials ◽  
Basis Sets ◽  
Excitation Energies ◽  
Transition Dipole ◽  
Vertical Excitation ◽  
Cluster Configuration

The properties of the ground and excited states of AsH2 , [Formula: see text] and [Formula: see text] have been investigated by using symmetry-adapted-cluster (SAC)/symmetry-adapted-cluster configuration interaction (SAC-CI) method. The geometry of the ground state of AsH2 is optimized at SAC method with different basis sets. The calculated results with cc-pVTZ and cc-pVQZ basis sets are in very good agreement with the experimental and previous theoretical data. The geometry and the properties of eight low-lying electronic excited states of AsH2 are obtained at SAC-CI/cc-pVTZ and SAC-CI/cc-pVQZ level, including geometries, vertical excitation energies, adiabatic excitation energies, transition dipole moments, and oscillation strengths. Employing the same theoretical level as AsH2 , the geometries, adiabatic ionization potentials (AIPs), and vertical ionization potentials (VIPs) of the ground and eight low-lying electronic states of [Formula: see text] are investigated as well as the geometries, vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) of nine electronic states of [Formula: see text]. Comparing with the available experimental or previous theoretical data, the SAC/SAC-CI/cc-pVTZ and SAC/SAC-CI/cc-pVQZ results are reliable for AsH2 , [Formula: see text] and [Formula: see text]. The predicted results can afford the useful information for one to deeply investigate them from the spectral experiment.

Sign in / Sign up

Export Citation Format

Share Document