Optical Observations of the Stark Effect on Oh

Phelps, D. H.; Dalby, F. W.

doi:10.1139/p65-013

Cited by 28 publications

(14 citation statements)

References 11 publications

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“…The total energies, dipole moments, and polarizabilities obtained with both the POLl and AN0 basis sets at the experimental geometries (35) using various methods are summarized in Table 3, and compared with the available experimental values (47)(48)(49)(50)(51)(52) in the case of dipole moments. These results enable us to draw a number of interesting conclusions concerning the role of the correlation effects, the use of relaxed (R) vs. nonrelaxed (N) orbitals, and the size of the basis set employed.…”

Section: Resultsmentioning

confidence: 99%

Calculation of static molecular properties in the framework of the unitary group based coupled cluster approach

Paldus¹,

Li²

1996

Can. J. Chem.

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The recently developed and implemented state selective, fully spin-adapted coupled cluster (CC) method that employs a single, yet effectively multiconfigurational, spin-free reference and the formalism of the unitary group approach (UGA) to the many-electron correlation problem, has been employed to calculate static electric properties of various open-shell ( 0 s ) systems using the finite field (FF) technique. Starting with the lithium atom, the method was applied at the first-order interacting space single and double excitation level (CCSD(is)) to several first-and second-row hydrides having OS ground state, namely to the CH, NH, OH, SiH, PH, and SH radicals. In the case of NH we also considered three OS excited states. In all cases the dipole moment and polarizability were determined using a high quality basis set and compared with the experiment, whenever available, as well as with various configuration interaction results and other theoretical results that are available from the literature. The agreement of our CCSD(is) values with experiment is very satisfactory except for the 3~-ground state of the NH radical, where the experimentally determined dipole moment is too small. No experimental data are available for the corresponding polarizabilities. It is also shown that the FF technique is not suitable for calculations of higher order static properties, such as the hyperpolarizability P and y tensors. For this reason we formulate the linear response version of our UGA-based CCSD approach and discuss the aspects of its future implementation.Key words: static molecular properties, dipole moments, polarizabilities, free radicals, unitary group based coupled cluster method, linear response theory, finite field technique.RCsurnC : On a utilisk la mtthode des cccoupled cluster,, (((CCn) complktement adaptCe aux spin et sClective des Ctats, dCveloppCe et mise en place rkcemment, qui n'utilise qu'une rCfCrence sans spin, mais qui est malgrC tout effectivement multiconfigurationnelle, ainsi que le formalisme de groups unitaires (NUGAD) au problkme de la corrClation de plusieurs Clectrons pour calculer les propriCtCs statiques de divers systernes en couches ouvertes (c

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Section: Resultsmentioning

confidence: 99%

Calculation of static molecular properties in the framework of the unitary group based coupled cluster approach

Paldus¹,

Li²

1996

Can. J. Chem.

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“…The resulting dipole moments for OH and OD are shown in Table 1. These values were found using best-fit slopes, weighted for error, according to the method of Phelps and Dalby (1965), as exemplified by the case of OD, v = 0 which is shown in Fig. 4.…”

Section: Resultsmentioning

confidence: 99%

“…tion. Although the 'll state exhibits intermediate coupling between Hund's case (a) and case (b) Theoretical coupling models (Hill and Van Vleck 1928), the An electric field E interacting with a dipole level J = 112 is pure case (a) and has a secondmoment p gives rise to a perturbing term in the order shift (see Phelps and Dalby (1965)) given by Can. J. Phys.…”

Section: Introductionmentioning

confidence: 99%

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High-Field Stark Effects on the Near Ultraviolet Spectrum of the Hydroxyl Radical

Scarl¹,

Dalby²

1971

Can. J. Phys.

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Spectra due to the A Z Z + -X Z n transition of the hydroxyl radical in electric fields of over 300 000 V per cm have been obtained. The dipole moment of the AZE+ v = 0 state of O H has been determined to be (1.98 + 0.08) D. From the variation of the dipole moment with vibrational quantum number in the state, the transition probability for the pure vibrational transition v = 1 -+ v = 0 has been estimated to be A,, = 80s-'.Les spectres des transitions provenant de 1'Ctat A Z Z + -X Z n du radical hydroxyle dans des champs electriques depassant 300 000 V par cm ont ete obtenus. Pour le moment dipolaire de 1'6tat AZE+ v = 0 de OH, on a trouve (1.98 + 0.08) D. A partir de la variation du moment de dip6le avec le nornbre quantique vibrationnel dans 1'Ctat on a estime a 80 s-' la probabilite de la transition vibrationnelle v = l -+ v = O .

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“…Only when in an electronic transition band there are very sharp lines as in the resolvable rotational fine structure of vaporized molecules, a direct observation of a shift may be possible in the visible or near ultraviolet range, as has been demonstrated in absorption spectra by Klemperer et al [3,41 and in emission spectra by Dalby et al [2]. But even in these favorable cases one cannot observe in an applied electric field a shift of lines corresponding to transitions between individual levels, but rather a broadening and splitting of a rotational line due to blending of different transitions between different close spaced levels.…”

Section: Berichte Der Bunsen-gesellschaftmentioning

confidence: 92%

Optical Absorption of Molecules in Liquid Solutions in an Applied External Electric Field (Electrochromism)

Liptay¹

1976

Ber Bunsenges Phys Chem

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A sufficiently strong applied electric field causes a shift and splitting of absorption and emission lines in atomic spectroscopy well known as Stark effect. With molecules usually only a field dependent change of the absorption and emission coefficient can be observed, a phenomenon called electrochromism. The various reasons which contribute to electrochromism are treated in this paper. Emphasized are the effects of the solvent molecules on the effective electric field causing additional contributions to electrochromism in solutions or other dense media compared to electrochromism in a gaseous phase.

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Optical Observations of the Stark Effect on Oh

Cited by 28 publications

References 11 publications

Calculation of static molecular properties in the framework of the unitary group based coupled cluster approach

Calculation of static molecular properties in the framework of the unitary group based coupled cluster approach

High-Field Stark Effects on the Near Ultraviolet Spectrum of the Hydroxyl Radical

Optical Absorption of Molecules in Liquid Solutions in an Applied External Electric Field (Electrochromism)

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