Matrix infrared spectra of the products of the phosphorus (P2) and ozone reaction

McCluskey, Matthew; Andrews, Lester

doi:10.1021/j100161a011

Cited by 25 publications

(20 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It is just noted here that the vibrational analyses of the two spectroscopic studies have not included any hot bands. Finally, we will ignore results of spectroscopic studies on PO 2 in matrices − for the time being and focus on the available gas-phase electronic spectra discussed above, which are quite complex. At the moment, it seems that considering the absorption spectrum assigned to be due to PO 2 in solid Ar 16 would not help in unraveling the complexity of the much better resolved gas-phase LIF and SVL emission spectra of Lei et al…”

Section: Introductionmentioning

confidence: 99%

Ab Initio Calculations on PO₂ and Anharmonic Franck−Condon Simulations of Its Single-Vibrational-Level Emission Spectra

et al. 2002

View full text Add to dashboard Cite

Geometry optimization and harmonic vibrational frequency calculations were carried out on some low-lying electronic states of PO 2 at the CIS, CASSCF, MP2, and RCCSD(T) levels with various standard basis sets of at least valence triple-ζ quality. Relative electronic energies, including vertical excitation energies from the X ˜2A 1 state {with the electronic configuration of ...(7a 1 ) 2 (8a 1 ) 1 } and T e values, were computed at the RCCSD(T) and CASSCF/MRCI levels with basis sets of up to aug-cc-pVQZ quality. These computed results, particularly the computed T e values, suggest that the upper electronic state of the laser induced fluorescence (LIF) and single-vibrational-level (SVL) emission spectra of PO 2 reported recently by Lei et al. [J. Phys. Chem. A 2001, 105, 7828] is the 2 2 A 1 state of PO 2 {with the electronic configuration of ...(7a 1 ) 1 (8a 1 ) 2 }. RCCSD(T)/ aug-cc-pVQZ and CASSCF/MRCI/aug-cc-pVQZ(no g) energy scans were carried out on the X ˜2A 1 and 2 2 A 1 states of PO 2 , respectively, in the symmetric stretching and bending coordinates. Franck-Condon factors (FCFs) between the two states, which allow for the Duschinsky and anharmonic effects, were calculated employing the potential energy functions obtained from the ab initio scans. Comparison between the simulated spectra based on the computed FCFs and observed SVL emission spectra led to reassignments of the vibrational designations of the emitting SVLs in the upper state. On the basis of the excellent agreement between the simulated spectra for the revised SVLs and the observed emission spectra, the electronic transition involved in the LIF and SVL emission spectra reported by Lei et al. is confirmed to be 2 2 A 2 -X ˜2A 1 of PO 2 . Following the revised vibrational assignments of the upper electronic state in the SVL emissions, the vibrational assignments of the LIF excitation bands given by Lei et al. are revised and a revised T 0 value of 30660 cm -1 is estimated for the 2 2 A 1 state of PO 2 . In addition, employing the iterative Franck-Condon analysis (IFCA) procedure in the simulation of the SVL emission spectra, the equilibrium geometry of the 2 2 A 1 state of PO 2 is derived for the first time (r e ) 1.560 Å; θ e ) 116.5°).

show abstract

Section: Introductionmentioning

confidence: 99%

Ab Initio Calculations on PO₂ and Anharmonic Franck−Condon Simulations of Its Single-Vibrational-Level Emission Spectra

et al. 2002

View full text Add to dashboard Cite

show abstract

“…A variety of spectroscopic techniques have been applied to phosphorus-containing materials. Laser and flash discharge experiments have been used to characterize gas phase PO and PO 2 . − Andrews and his co-workers have carried out low-temperature matrix experiments in which they assign infrared absorptions to more than two dozen species in the P−O−H system. − Data on the spectroscopy of the higher oxides including the stable species P 4 O 6 and P 4 O 10 are surprisingly sparse. Infrared absorption and Raman spectra of P 4 O 6 and P 4 O 10 at room temperature have been reported and vibrational assignments have been made for each molecule. − Konings et al have measured the infrared spectrum of gas phase P 4 O 10 at elevated temperature .…”

Section: Introductionmentioning

confidence: 99%

Vibrational Analysis of P₄O₆and P₄O₁₀

1997

View full text Add to dashboard Cite

The equilibrium geometries, vibrational frequencies, and infrared and Raman intensities for P4O6 and P4O10 were calculated using the Hartree−Fock self-consistent-field method. The computed geometries are in good agreement with experimental measurements. Scaling the ab initio vibrational frequencies of P4O10 to account for anharmonicity and neglect of electron correlation yields values that agree with experimentally observed transitions, confirming the previous assignment of the spectrum. The energy ordering of the computed vibrational levels for P4O6 differs, in part, from assignments based on experimental data. A new assignment that is in agreement with both the computations and the experiments is suggested; this requires the reassignment of four of the fundamental vibrations. The infrared emission spectrum produced by burning red phosphorus in air was recorded and the observed peaks assigned to P4O10 transitions. The experimental relative intensities of the fundamental vibrations agree well with the computed relative intensities.

show abstract

“…In previous P 2 oxidation experiments from this laboratory, , bands at 1438.4, 1168.1, and 955.4 cm -l (labeled Y in the previous work) were assigned to oxo-bridged P 2 O 4 (i.e., O 2 P−O−PO). These bands are not observed in the present experiments, but the strongest calculated bands (Table ) are compatible with this assignment.…”

Section: Resultsmentioning

confidence: 83%

“…The strong sharp 1319.0 cm -1 absorption has been assigned to the antisymmetric stretching fundamental (ν 3 ) of PO 2 in solid argon. ,− This absorption is red-shifted 8.5 cm -1 from the gas-phase diode laser value of 1327.53 cm -l . The reaction with 18 O 2 displaces the 1319.0 cm -1 absorption to 1280.0 cm -1 .…”

Section: Resultsmentioning

confidence: 99%

“…They also tentatively assigned a band at 435.2 cm -1 as the e′ bending mode of the same molecule. The assignment was based in large part on the spectra with mixed 16,18 O, which clearly showed that the a 2 ′′ mode arose from a species with three equivalent oxygen atoms, and on the fact that using PD 3 , instead of PH 3 , showed that the species did not include any hydrogen.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A Study of the Products of the Reaction of Phosphorus and Dioxygen

2000

Self Cite

View full text Add to dashboard Cite

show abstract

Matrix infrared spectra of the products of the phosphorus (P2) and ozone reaction

Cited by 25 publications

References 2 publications

Ab Initio Calculations on PO₂ and Anharmonic Franck−Condon Simulations of Its Single-Vibrational-Level Emission Spectra

Ab Initio Calculations on PO₂ and Anharmonic Franck−Condon Simulations of Its Single-Vibrational-Level Emission Spectra

Vibrational Analysis of P₄O₆and P₄O₁₀

A Study of the Products of the Reaction of Phosphorus and Dioxygen

Contact Info

Product

Resources

About

Matrix infrared spectra of the products of the phosphorus (P2) and ozone reaction

Cited by 25 publications

References 2 publications

Ab Initio Calculations on PO2 and Anharmonic Franck−Condon Simulations of Its Single-Vibrational-Level Emission Spectra

Ab Initio Calculations on PO2 and Anharmonic Franck−Condon Simulations of Its Single-Vibrational-Level Emission Spectra

Vibrational Analysis of P4O6and P4O10

A Study of the Products of the Reaction of Phosphorus and Dioxygen

Contact Info

Product

Resources

About

Ab Initio Calculations on PO₂ and Anharmonic Franck−Condon Simulations of Its Single-Vibrational-Level Emission Spectra

Ab Initio Calculations on PO₂ and Anharmonic Franck−Condon Simulations of Its Single-Vibrational-Level Emission Spectra

Vibrational Analysis of P₄O₆and P₄O₁₀