ULTRAVIOLET SPECTRA OF LiH AND LiD

1957 ◽  
Vol 35 (10) ◽  
pp. 1204-1214 ◽  
Author(s):  
R. Velasco
Keyword(s):  
Excited State ◽  
Ground State ◽  
Band System ◽  
Electronic States ◽  
High Dispersion ◽  
Dissociation Energies ◽  
Near Ultraviolet ◽  
Path Lengths ◽  
Vibrational Constants ◽  
Π State

The absorption spectra of LiH and LiD have been observed in the near ultraviolet with high dispersion and absorbing path lengths up to 16 meters. A new band system has been found in each molecule involving the ground state and a 1Π excited state. Rotational and vibrational analyses of this system have been carried out and rotational and vibrational constants for the upper state have been determined. The observed breaking off of the rotational structure of the bands of this B1Π—X1Σ+ system has been interpreted as due to predissociation by rotation. With this assumption very accurate dissociation limits of the B1Π state have been obtained. From these dissociation limits the dissociation energies of the three known electronic states of LiH and LiD have been calculated. In particular the dissociation energies (D0) of the ground states of LiH and LiD have been found to be 2.4288 ± 0.0002 ev. and 2.4509 ± 0.0010 ev., respectively.

ROTATIONAL ANALYSIS OF THE β BANDS OF PHOSPHORUS MONOXIDE

1959 ◽  
Vol 37 (2) ◽  
pp. 136-143 ◽  
Author(s):  
Nand Lal Singh
Keyword(s):  
Ground State ◽  
Band System ◽  
Electronic States ◽  
Rotational Analysis ◽  
Rotational Constants ◽  
Fine Structures ◽  
Π State

The fine structures of three of the β bands of PO which occur near 3200 Å have been analyzed. The analysis shows that the upper state of this band system is a 2Σ and not a 2Π state as previously believed. The rotational constants of both electronic states have been determined and it is found that the ground state constants, previously determined from the γ bands, are incorrect.

THE ABSORPTION SPECTRUM OF CF2

1967 ◽  
Vol 45 (7) ◽  
pp. 2355-2374 ◽  
Author(s):  
C. Weldon Mathews
Keyword(s):  
Absorption Spectrum ◽  
Electronic State ◽  
Ground State ◽  
Band System ◽  
Electronic States ◽  
Vibrational Structure ◽  
Rotational Structure ◽  
Transition Moment ◽  
High Dispersion ◽  
Parallel Type

The absorption spectrum of CF2 in the 2 500 Å region has been photographed at high dispersion, and the rotational structure of a number of bands has been analyzed. The analysis of the well-resolved subbands establishes that these are perpendicular- rather than parallel-type bands, as previously assigned. Further analysis shows that the upper and lower electronic states are of 1B1 and 1A1symmetries respectively, corresponding to a transition moment that is perpendicular to the plane of the molecule. In the upper electronic state, r0(CF) = 1.32 Å and [Formula: see text], while in the ground state, r0(CF) = 1.300 Å and [Formula: see text]. An investigation of the vibrational structure of the band system has shown that the vibrational numbering in ν2′ must be increased by one unit from earlier assignments, thus placing the 000–000 band near 2 687 Å (37 220 cm−1). A search between 1 300 and 8 500 Å showed two new band systems near 1 350 and 1 500 Å which have been assigned tentatively to the CF2 molecule.

The Ground State and A2Π Excited State of Magnesium Deuteride

1975 ◽  
Vol 53 (15) ◽  
pp. 1477-1482 ◽  
Author(s):  
Walter J. Balfour ◽  
Hugh M. Cartwright
Keyword(s):  
Excited State ◽  
High Resolution ◽  
Emission Spectrum ◽  
Isotope Effect ◽  
Ground State ◽  
Visible Emission ◽  
Molecular Constants ◽  
Dissociation Energies ◽  
First Time ◽  
Π State

The visible emission spectrum of MgD has been reexamined at high resolution. Published analyses of the A2Π → X2Σ+ system have been extended and the data have been combined with observations in the B′2Σ+ → X2Σ+ system to provide information on the ground state levels ν = 3, 4, 5, and 6 for the first time. The following molecular constants (in cm−1) have been determined—for the A2Π state: ωc = 1154.75, ωcxc = 16.675, Bc = 3.2190, Dc = 9.64 × 10−5 and for the X2Σ+ state: ωc = 1077.71, ωcxc = 15.92, Bc = 3.0306, and Dc = 9.39 × 10−5. The dissociation energies in the A2Π and X2Σ+ states have been estimated to be ~ 15 500 cm−1 and ~ 11 500 cm−1 respectively. The MgH/MgD isotope effect and the Λ doubling in the A2Π state are discussed.

THE ABSORPTION SPECTRUM OF SH AND SD IN THE VACUUM ULTRAVIOLET

1966 ◽  
Vol 44 (10) ◽  
pp. 2447-2459 ◽  
Author(s):  
B. A. Morrow
Keyword(s):  
Absorption Spectrum ◽  
Excited State ◽  
Excited States ◽  
Ground State ◽  
Vacuum Ultraviolet ◽  
Flash Photolysis ◽  
Electronic States ◽  
Rydberg Series ◽  
A Value ◽  
Vibrational Constants

The absorption spectrum of SH in the vacuum ultraviolet has been obtained by the flash photolysis of hydrogen sulfide. Transitions from the 2Π ground state to seven excited states have been observed and four of these fit reasonably well into a Rydberg series. From an extrapolation to the convergence limit of this series, a value of 10.40 ± 0.03 eV for the ionization potential of SH has been derived. Values for the rotational constants of these new electronic states have been determined; corresponding data for SD have also been obtained. The (1–0) transition of the system near 1 670 Å (B2Σ–X2Π) was observed, and, with the aid of isotope relations, vibrational constants of the B state have been derived. An estimate of the dissociation energy of SH in this excited state is D0′ = 24 190 ± 1 000 cm−1.

The 4550 Å band system of glyoxal. IV. Vibration–rotational analyses for 11 bands of 13C2H2O2 and determination of molecular geometries

1977 ◽  
Vol 55 (5) ◽  
pp. 390-395 ◽  
Author(s):  
F. W. Birss ◽  
D. B. Braund ◽  
A. R. H. Cole ◽  
R. Engleman Jr. ◽  
A. A. Green ◽  
...  
Keyword(s):  
Excited State ◽  
Electron Diffraction ◽  
Excellent Agreement ◽  
Ground State ◽  
Band System ◽  
Vibrational Frequencies ◽  
Geometrical Parameters ◽  
Rotational Constants ◽  
Vibrational Constants

Rotational analyses have been carried out for 11 bands of the [Formula: see text](π*–n) system of 13C2H2O2 in absorption. Approximately 12 000 lines have been assigned, and rotational and vibrational constants have been evaluated. The following vibrational frequencies have been determined: ν2′ = 1365.17 cm−1, ν4′ = 918.81 cm−1, ν5′ = 502.48 cm−1, ν7′ = 229.40 cm−1, ν7″ = 124.61 cm−1Using the rotational constants for C2H2O2, C2HDO2, C2D2O2, 13C2H2O2, and C2H218O2, the following geometrical parameters have been evaluated: in the Ã1Au excited state, r0(CH) = 1.115 ± 0.010 Å, r0(CO) = 1.252 ± 0.016 Å, r0(CC) = 1.460 ± 0.025 Å, [Formula: see text], [Formula: see text]; in the [Formula: see text] ground state, r0(CH) = 1.109 ± 0.008 Å, r0(CO) = 1.202 ± 0.012 Å, r0(CC) = 1.527 ± 0.017 Å, [Formula: see text], [Formula: see text]. The ground state parameters are in excellent agreement with earlier electron diffraction results.

Excited-State Dynamics in the RNA Nucleotide Uridine 5’-Monophosphate Investigated by Femtosecond Broadband Transient Absorption Spectroscopy

2019 ◽  
Author(s):  
Matthew M. Brister ◽  
Carlos Crespo-Hernández
Keyword(s):  
Excited State ◽  
Excited States ◽  
Ground State ◽  
Transient Absorption ◽  
Electronic Energy ◽  
Transient Absorption Spectroscopy ◽  
Electronic Relaxation ◽  
Vibrationally Excited ◽  
Excited State Dynamics ◽  
Π State

<p></p><p> Damage to RNA from ultraviolet radiation induce chemical modifications to the nucleobases. Unraveling the excited states involved in these reactions is essential, but investigations aimed at understanding the electronic-energy relaxation pathways of the RNA nucleotide uridine 5’-monophosphate (UMP) have not received enough attention. In this Letter, the excited-state dynamics of UMP is investigated in aqueous solution. Excitation at 267 nm results in a trifurcation event that leads to the simultaneous population of the vibrationally-excited ground state, a longlived <sup>1</sup>n<sub>O</sub>π* state, and a receiver triplet state within 200 fs. The receiver state internally convert to the long-lived <sup>3</sup>ππ* state in an ultrafast time scale. The results elucidate the electronic relaxation pathways and clarify earlier transient absorption experiments performed for uracil derivatives in solution. This mechanistic information is important because long-lived nπ* and ππ* excited states of both singlet and triplet multiplicities are thought to lead to the formation of harmful photoproducts.</p><p></p>

Vibrational Analysis of the 2800 Å Band System of para-Dibromobenzene

1972 ◽  
Vol 50 (12) ◽  
pp. 1402-1408 ◽  
Author(s):  
S. M. Japar
Keyword(s):  
Excited State ◽  
High Resolution ◽  
Ground State ◽  
Band System ◽  
Vibrational Analysis ◽  
Type A ◽  
Strong Type ◽  
Type B ◽  
Sequence Structure ◽  
Extensive Sequence

The 2800 Å band system of p-dibromobenzene has been photographed under high resolution and an extended vibrational analysis has been carried out. The analysis is not inconsistent with the assignment of the system to a 1B2u ← 1Ag transition, by analogy with other p-dihalogenated benzenes. The observed spectrum can be explained in terms of a number of strong type-B vibronic bands and a considerably smaller number of type-A vibronic bands. The extensive sequence structure is adequately accounted for, and can be related to observations on other halogenated benzene molecules. Thirteen ground state and nine excited state fundamental vibrational frequencies have been assigned.

THE b1Σ+–X3Σ− BAND SYSTEM OF NF

1966 ◽  
Vol 44 (10) ◽  
pp. 2251-2258 ◽  
Author(s):  
A. E. Douglas ◽  
W. E. Jones
Keyword(s):  
Ground State ◽  
Band System ◽  
High Dispersion ◽  
Rotational Analysis ◽  
Strong Band

If argon mixed with a small amount of NF3 is pumped rapidly through a mild discharge, a green glow is observed downstream from the discharge. This emission has been photographed with a high dispersion spectrograph and found to consist of a strong band with a head at 5 288 Å and a number of weaker bands. A rotational analysis of the bands has shown that they are the b1Σ+–X3Σ− bands of the NF molecule. The constants of the two states have been determined and it is found that for the ground state, ωe = 1 141.37 cm−1 and re = 1.317 3 Å.

A NEW BAND SYSTEM OF THE P2 MOLECULE ANALOGOUS TO THE LYMAN–BIRGE–HOPFIELD BANDS OF N2

1958 ◽  
Vol 36 (5) ◽  
pp. 565-570 ◽  
Author(s):  
A. E. Douglas ◽  
K. Suryanarayana Rao
Keyword(s):  
Excited States ◽  
Ground State ◽  
Singlet State ◽  
Band System ◽  
Excited Singlet State ◽  
Lower State ◽  
High Dispersion ◽  
Electron Configuration ◽  
Excited Singlet ◽  
New System

Five bands of a new band system of P2 have been photographed at high dispersion and analyzed. The upper state of the system is a 1П0 state and lies lower than any previously known excited singlet state. The lower state of the new system is the ground state of P2 and the analysis of the new bands has given improved constants for this state. The new system appears to be the analogue of the Lyman–Birge–Hopfield bands of N2. The electron configuration of the low excited states of P2 and of related molecules is discussed.

The analysis of a 2 A 1 - 2 B 1 electronic band system of the AsH 2 and AsD 2 radicals

1968 ◽  
Vol 305 (1481) ◽  
pp. 271-290 ◽  
Keyword(s):  
Excited State ◽  
Ground State ◽  
Flash Photolysis ◽  
Band System ◽  
Valence Angle ◽  
Electronic Transitions ◽  
Doublet State ◽  
Electronic Band ◽  
Asymmetric Rotor ◽  
Asymmetric Top

Two new band systems have been observed in absorption following flash photolysis of AsH 3 and AsD 3 , and are assigned to 2 A 1 - 2 B 1 electronic transitions of AsH 2 and AsD 2 . The origins of both systems are at 19905 cm -1 . The bands have the complex rotational structure associated with an asymmetric rotor. Rotational analyses have been carried out for three bands of the AsH 2 spectrum, leading to the following molecular parameters: ground state, r" 0 = 1.518 Å valence angle = 90° 44'; excited state, r' 0 = 1.48 Å, valence angle = 123° 0'. The parameters associated with rotation about the a inertial axis increase rapidly with increase in v' 2 . The spectrum shows doublet splittings of up to 41 cm -1 , and the excited state furnishes the first example of a doublet state of an asymmetric top molecule which shows substantial departures from Hund’s case ( b ).

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