The spectrum and structure of the He2 molecule: Characterization of the triplet states associated with the UAO's 4pπ and 5pπ

The He₂ band systems $\text{4pπ i}{}^3\text{Π}{}_{\mathrm{g}}\text{→ 2s a}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ and $\text{5pπ l}{}^3\text{Π}{}_{\mathrm{g}}\text{→ 2s a}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ are described in detail, and the i and l states characterized. A number of significant perturbations in the i and l states are identified, and the possible perturber states discussed. The following molecular constants (cm^?1) are reported:

     

9.

Computer simulation of some field-induced phenomena of molecular liquids     

Myron W. Evans 《Journal of Molecular Liquids》1983,26(1):49-61

     

10.

Deperturbation study of the 0_u⁺ symmetry states of As₂ observed in the energy range 39 000–45 000 cm⁻¹     

Pierre Perdigon  Françoise Martin 《Journal of Molecular Spectroscopy》1980,83(1):40-63

The mutual perturbations of the A¹Σ_u⁺ and b0_u⁺ states of As₂ are due to a strong spin-orbit interaction. The numerical treatment of these perturbations leads to the following parameters:

State	$\text{ω}{}_{\mathrm{e}}$	$\text{xω}{}_{\mathrm{e}}$	$\text{B}{}_{\mathrm{e}}$	$\text{α}{}_{\mathrm{e}}$	$\text{r}{}_{\mathrm{e}}\text{(}\text{A}\text{?}\text{)}$
$\text{i}{}^3\text{Π}{}_{\mathrm{g}}$	1707.95	35.00	7.242g	0.222	1.0782
$\text{l}{}^2\text{Π}{}_{\mathrm{g}}$	1703.86	34.97	7.2264	0.2188	1.0794

     

11.

Statistical methods in classical mechanics     

Jerzy Hańćkowiak 《Reports on Mathematical Physics》1975,7(2):239-249

     

12.

The emission spectrum of SeO in the far ultraviolet     

S.Paddi Reddy  M. Azam 《Journal of Molecular Spectroscopy》1974,49(3):461-467

The emission spectrum of SeO in the far ultraviolet first observed by Haranath (1) at low dispersion has been photographed in the region 2480-1930 Å under medium resolution and a reanalysis of the vibrational structure of the bands has been presented. Beginning at the longer wavelength end, the spectrum has been analyzed into five band systems which are designated as $\text{c(}{}^1\text{Σ}{}^{\mathrm{+}}\text{)-b(}{}^1\text{Σ}{}^{\mathrm{+}}\text{)}$, x₂-x₁, y₂-y₁, $\text{C(}{}^3\text{Π}\text{)-X}{}^3\text{Σ}{}^{\mathrm{?}}$, and $\text{D(}{}^3\text{Σ}{}^{\mathrm{?}}\text{)-X}{}^3\text{Σ}{}^{\mathrm{?}}$. The lower state of the c-b system is found to be the upper state of the $\text{b(}{}^1\text{Σ}{}^{\mathrm{+}}\text{)-X}{}^3\text{Σ}{}^{\mathrm{?}}$ system observed recently by us (2). The derived constants in cm^?1 for SeO are as follows (the constants of the b state are those derived from Ref. 2).

	$\text{T}{}_{\mathrm{e}}\text{(}\text{cm}{}^{\mathrm{?1}}\text{)}$	$\text{ω}{}_{\mathrm{e}}\text{(}\text{cm}{}^{\mathrm{?1}}\text{)}$	$\text{ω}{}_{\mathrm{e}}\text{x}{}_{\mathrm{e}}\text{(}\text{cm}{}^{\mathrm{?1}}\text{)}$	$\text{B}{}_{\mathrm{e}}\text{(}\text{cm}{}^{\mathrm{?1}}\text{)}$
$\text{A}{}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$	40 806 (3)	297 (2)	5.1 (2)	0.0798 (12)
$\text{b0}{}_{\mathrm{u}}{}^{\mathrm{+}}$	38 884 (3)	422 (1)	8.8 (1)	0.0783 (12)

     

13.

The electronic isotope shift in the A²Π-X²Σ⁺ bands of BeH,BeD and BeT     

D. De Greef  R. Colin 《Journal of Molecular Spectroscopy》1974,53(3):455-465

The 0-0, 1-1, 2-2, and 3-3 bands of the A²Π-X²Σ⁺ transition of the tritiated beryllium monohydride molecule have been observed at 5000 Å in emission using a beryllium hollow-cathode discharge in a He + T₂ mixture. The rotational analysis of these bands yields the following principal molecular constants.

$\text{A}{}^2\text{Π:}\text{B}{}_{\mathrm{e}}\text{= 4.192}\text{cm}{}^{\mathrm{?1}}\text{; r}{}_{\mathrm{e}}\text{= 1.333}\text{A}\text{?}$

$\text{X}{}^2\text{Σ:}\text{B}{}_{\mathrm{e}}\text{= 4.142}\text{cm}{}^{\mathrm{?1}}\text{; r}{}_{\mathrm{e}}\text{= 1.341}\text{A}\text{?}$

$\text{ω}{}_{\mathrm{e}}\text{′ ? ω}{}_{\mathrm{e}}\text{″ = 16.36}\text{cm}{}^{\mathrm{?1}}\text{; ω}{}_{\mathrm{e}}\text{′X}{}_{\mathrm{e}}\text{′ ? ω}{}_{\mathrm{e}}\text{″X}{}_{\mathrm{e}}\text{″ = 0.84}\text{cm}{}^{\mathrm{?1}}$

From the pure electronic energy difference (E_Π - E_Σ)_BeT = 20 037.91 ± 1.5 cm^?1 and the corresponding previously known values for BeH and BeD, the following electronic isotope shifts are derived

$\text{ΔE}{}_{\mathrm{e}}{}^{\mathrm{i}}\text{(}\text{BeH}\text{?}\text{BeT}\text{) = ?4.7 ≠ 1.5}\text{cm}{}^1\text{, ΔE}{}_{\mathrm{e}}{}^{\mathrm{i}}\text{(}\text{BeH}\text{?}\text{BeT}\text{) = ?1.8 ≠ 1.5}\text{cm}{}^1$

and related to the theoretical approach given by Bunker to the problem of the breakdown of the Born-Oppenheimer approximation.     

14.

Ar⁺ laser-induced fluorescence spectra of Cs₂: The E¹Σ_u⁺ and (1) ¹Π_g electronic states     

C. Amiot  C. Crépin  J. Vergès 《Journal of Molecular Spectroscopy》1984,107(1):28-47

Laser-induced fluorescence of Cs₂ molecules in the infrared (1.15–2.5 μm) and the visible (505–545 nm) regions has been observed using several excitation wavelengths from an argonion laser. Accurate molecular constants and potential energy curves for the pumped E¹Σ_u⁺ state and the first excited gerade ¹Π state are derived from more than 1300 fluorescence lines precisely measured with a high-resolution Fourier transform interferometer. The main molecular constants for the states are

State	$\text{T}{}_{\mathrm{e}}$	$\text{ω}{}_{\mathrm{e}}$	$\text{ω}{}_{\mathrm{e}}\text{x}{}_{\mathrm{e}}$	λ
$\text{y}{}_2$	$\text{y}{}_1\text{+ 47830}$	974	6.0
$\text{y}{}_1$	$\text{y}{}_1$	906	21.0
$\text{x}{}_2$	$\text{x}{}_1\text{+ 46009}$	993	2.0
$\text{x}{}_1$	$\text{x}{}_1$	877	8.0
$\text{c(}{}^1\text{Σ}{}^{\mathrm{+}}\text{)}$	53080	954	13.0
$\text{D(}{}^3\text{Σ}{}^{\mathrm{?}}\text{)}\text{F}{}_2$	51422	955	9.3
F1	51356	955	8.5	～36
$\text{C(}{}^3\text{Π}\text{)}$	50873	1034	9.3
$\text{b(}{}^1\text{Σ}{}^{\mathrm{+}}\text{)}$	9570.7	834.9	5.5

     

15.

Quantum mechanics in phase space     

F. Hansen 《Reports on Mathematical Physics》1984,19(3):361-381

     

16.

The A²Π-X²Π system of the SbO molecule     

Walter J Balfour  Ram S Ram 《Journal of Molecular Spectroscopy》1984,105(1):246-259

The emission spectrum of the A²Π-X²Π system of the SbO molecule has been photographed under high resolution, and the rotational structure in eight bands of the ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ component, involving v′ = 0–2 and v″ = 1–4, has been analyzed for both isotopic molecules ¹²¹SbO and ¹²³SbO. The observed rotational lines of the corresponding ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ component are broad, with a width of about 0.2 cm^?1 varying little with J. It is suggested that these broad lines represent unresolved components arising from magnetic hyperfine interaction with ¹²¹Sb or ¹²³Sb nuclei. Isotopic shift observations contradict earlier vibrational assignments in the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ subsystem and indicate that the A state is inverted in agreement with expectations from related systems. The principal molecular constants (in cm^?1) obtained for ¹²¹SbO are

	$\text{T}{}_{\mathrm{e}}\text{(}\text{cm}{}^{\mathrm{?1}}\text{)}$	$\text{ω}{}_{\mathrm{e}}\text{(}\text{cm}{}^{\mathrm{?1}}\text{)}$	$\text{B}{}_{\mathrm{e}}\text{(}\text{cm}{}^{\mathrm{?1}}\text{)}$	$\text{R}{}_{\mathrm{e}}\text{(}\text{A}\text{?}\text{)}$
$\text{E}{}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$	20195.23	29.10	0.00891	5.340733
(1) ${}^1\text{Π}{}_{\mathrm{g}}$	13913.42	18.44	0.00781	5.697722

     

17.

High resolution Fourier spectroscopy of P2 infrared emission spectrum: Analysis of two new systems b3Πg → w3Δu and A1Πg → W1Δu     

C Amiot  C Effantin  J d&#x;Incan  J Verges 《Journal of Molecular Spectroscopy》1978,72(2):189-199

The investigation of the emission infrared spectrum of P₂ was performed with a high resolution Fourier spectrometer. Two new electronic systems were attributed to b³Π_g → w³Δ_u and A¹Π_g → W¹Δ_u transitions. The molecular parameters are obtained by a complete fitting procedure. The main equilibrium constants of the new states are (in cm^?1):

$\text{ω}{}^3\text{Δ}{}_{\mathrm{u}}\text{T}{}_{\mathrm{e}}\text{= 243228.07 ω}{}_{\mathrm{e}}\text{= 591.3 ω}{}_{\mathrm{e}}\text{X}{}_{\mathrm{e}}\text{= 2.5}$

$\text{B}{}_{\mathrm{e}}\text{= 0.256040 δ}{}_{\mathrm{e}}\text{= 0.001409 D}{}_{\mathrm{e}}\text{= 19.0 X 10}{}^{\mathrm{?8}}$

$\text{W}{}^1\text{Δ}{}_{\mathrm{u}}\text{T}{}_{\mathrm{e}}\text{= 31096.64 W}{}_{\mathrm{e}}\text{= 627.206 W}{}_{\mathrm{e}}\text{X}{}_{\mathrm{e}}\text{= 2.331}$

$\text{B}{}_{\mathrm{e}}\text{= 0.2628 δ}{}_{\mathrm{e}}\text{= 0.0014 D}{}_{\mathrm{e}}\text{= 23 X 10}{}^{\mathrm{?8}}$

     

18.

High-resolution laser excitation spectroscopy: Analysis of the B2Σ+-X2Σ+ system of CaCl     

Peter J. Domaille  Timothy C. Steimle  Ning Bew Wong  David O. Harris 《Journal of Molecular Spectroscopy》1977,65(3):354-365

Single-mode cw dye laser excitation spectra of the (0, 0), (1, 1), and (2, 2) bands of the B²Σ⁺-X²Σ⁺ system of CaCl have been observed and assigned. Some 300 independent photo-luminescence spectra have been used in making the rotational assignment and demonstrate the power of the technique of line-by-line analysis in unraveling complex spectra. Spectroscopic constants (cm^?1) obtained from a weighted least squares fit of the data are given below. Numbers in parentheses refer to 95% confidence limits in the last digit.

State	$\text{T}{}_{\mathrm{e}}$	$\text{ω}{}_{\mathrm{e}}$	$\text{ω}{}_{\mathrm{e}}\text{χ}{}_{\mathrm{e}}$	$\text{B}{}_{\mathrm{e}}$	$\text{10}{}^3\text{α}{}_{\mathrm{e}}$	$\text{10}{}^7\text{D}{}_{\mathrm{e}}$
$\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$	0	818.7	4.2	—	—	—
$\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$	x ≈ 2272	814.1	4.3	0.35920	2.38	2.8
$\text{A}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$	21 467.4	565.8	2.9	—	—	—
$\text{A}{}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$	x + 18 521.7	570.4	2.6	0.28856	1.82	2.9

     

19.

Vibration-rotation and deperturbation analysis of A²Π-X²Σ⁺ and B²Σ⁺-X²Σ⁺ systems of the CaI molecule     

David E Reisner  Peter F Bernath  R.W Field 《Journal of Molecular Spectroscopy》1981,89(1):107-124

Doppler-limited laser excitation spectroscopy employing narrow-band fluorescence detection was used to obtain a rotational and vibrational analysis in the (0, 0) and (1, 1) bands of the A²Π-X²Σ⁺ system and the (4, 2) (3, 1), (0, 0), (0, 1), (1, 2), (2, 3), and (3, 4) bands of the B²Σ⁺-X²Σ⁺ system of CaI. The A and B states are deperturbed to obtain spectroscopic constants and Franck-Condon factors. Deperturbation was necessary because of the small separation of the A and B states relative to the A ～ B interaction strength and the A²Π spin-orbit splitting. The main deperturbed constants (in cm^?1) are

	$\text{X}{}^2\text{Σ}{}^{\mathrm{+}}$	$\text{B}{}^2\text{Σ}{}^{\mathrm{+}}$
$\text{T}{}_{\mathrm{e}}$	0	16856.69(2)
$\text{ω}{}_{\mathrm{e}}$	369.8(10)	366.8(10)
$\text{ω}{}_{\mathrm{e}}\text{x}{}_{\mathrm{e}}$	1.13(20)	1.28(20)
$\text{B}{}_{\mathrm{e}}$	0.15200(54)	0.15448(54)
$\text{α}{}_{\mathrm{e}}$	0.00063(34)	0.00073(35)
$\text{D}{}_{\mathrm{e}}$	1.027(16) × 10?7	1.097(17) × 10?7
$\text{γ}{}_{\mathrm{e}}$ (spin-rotation)	+0.003	?0.0630(16)

     

20.

The A3Π-X0+, 1 band system of the SeO molecule     

K.K. Verma  M. Azam  S.Paddi Reddy 《Journal of Molecular Spectroscopy》1977,65(2):289-294

A new weak emission band system of the SeO molecule consisting of 34 band heads degraded to shorter wavelengths has been observed for the first time in the spectral region 6730–8570 Å. The vibrational analysis of the system suggests that it arises from the transition A³Π_reg-X0⁺, 1. All the five subsystems allowed by the selection rule $\text{ΔΩ}\text{= 0}$, ±1 have been identified. The constants in cm^?1 derived for the A³Π state are

	$\text{X}{}^2\text{Σ}{}^{\mathrm{+}}$	$\text{A}{}^2\text{Π}$	$\text{B}{}^2\text{Σ}{}^{\mathrm{+}}$
$\text{T}{}_{\mathrm{e}}$	0	15 624.67(5)	15 700.52(12)
$\text{ω}{}_{\mathrm{e}}$	238.7496(33)	241.19(7)	242.63(17)
$\text{ω}{}_{\mathrm{e}}\text{χ}{}_{\mathrm{e}}$	0.62789(64)	0.53(5) (Pekeris)	1.17(12) (Pekeris)
$\text{B}{}_{\mathrm{e}}$	0.0693254(84)	0.070460(14)	0.071572(22)
$\text{α}{}_{\mathrm{e}}\text{× 10}{}^4$	2.640(35)	2.15(10)	3.95(2)
$\text{A}{}_{\mathrm{e}}$	—	45.8968(52)	—
$\text{R}{}_{\mathrm{e}}\text{(}\text{A}\text{?}\text{)}$	2.8286(2)	2.8057(3)	2.7839(4)

     

	$\text{T}{}_{\mathrm{e}}$	$\text{ω}{}_{\mathrm{e}}$	$\text{ω}{}_{\mathrm{e}}\text{x}{}_{\mathrm{e}}$
$\text{A}{}_3{}^3\text{Π}{}_2$	16 758	$\text{Δ}\text{G(}\text{1}\text{2}\text{) = 980}$
$\text{A}{}_2{}^3\text{Π}{}_1$	16 442	996	7.0
$\text{A}{}_1{}^3\text{Π}{}_0$	16 131	994	6.5

Deperturbation study of the 0u+ symmetry states of As2 observed in the energy range 39 000–45 000 cm−1

The mutual perturbations of the A¹Σ_u⁺ and b0_u⁺ states of As₂ are due to a strong spin-orbit interaction. The numerical treatment of these perturbations leads to the following parameters:

The emission spectrum of SeO in the far ultraviolet

The emission spectrum of SeO in the far ultraviolet first observed by Haranath (1) at low dispersion has been photographed in the region 2480-1930 Å under medium resolution and a reanalysis of the vibrational structure of the bands has been presented. Beginning at the longer wavelength end, the spectrum has been analyzed into five band systems which are designated as $\text{c(}{}^1\text{Σ}{}^{\mathrm{+}}\text{)-b(}{}^1\text{Σ}{}^{\mathrm{+}}\text{)}$, x₂-x₁, y₂-y₁, $\text{C(}{}^3\text{Π}\text{)-X}{}^3\text{Σ}{}^{\mathrm{?}}$, and $\text{D(}{}^3\text{Σ}{}^{\mathrm{?}}\text{)-X}{}^3\text{Σ}{}^{\mathrm{?}}$. The lower state of the c-b system is found to be the upper state of the $\text{b(}{}^1\text{Σ}{}^{\mathrm{+}}\text{)-X}{}^3\text{Σ}{}^{\mathrm{?}}$ system observed recently by us (2). The derived constants in cm^?1 for SeO are as follows (the constants of the b state are those derived from Ref. 2).

The electronic isotope shift in the A2Π-X2Σ+ bands of BeH,BeD and BeT

The 0-0, 1-1, 2-2, and 3-3 bands of the A²Π-X²Σ⁺ transition of the tritiated beryllium monohydride molecule have been observed at 5000 Å in emission using a beryllium hollow-cathode discharge in a He + T₂ mixture. The rotational analysis of these bands yields the following principal molecular constants.

$\text{A}{}^2\text{Π:}\text{B}{}_{\mathrm{e}}\text{= 4.192}\text{cm}{}^{\mathrm{?1}}\text{; r}{}_{\mathrm{e}}\text{= 1.333}\text{A}\text{?}$

$\text{X}{}^2\text{Σ:}\text{B}{}_{\mathrm{e}}\text{= 4.142}\text{cm}{}^{\mathrm{?1}}\text{; r}{}_{\mathrm{e}}\text{= 1.341}\text{A}\text{?}$

$\text{ω}{}_{\mathrm{e}}\text{′ ? ω}{}_{\mathrm{e}}\text{″ = 16.36}\text{cm}{}^{\mathrm{?1}}\text{; ω}{}_{\mathrm{e}}\text{′X}{}_{\mathrm{e}}\text{′ ? ω}{}_{\mathrm{e}}\text{″X}{}_{\mathrm{e}}\text{″ = 0.84}\text{cm}{}^{\mathrm{?1}}$

From the pure electronic energy difference (E_Π - E_Σ)_BeT = 20 037.91 ± 1.5 cm^?1 and the corresponding previously known values for BeH and BeD, the following electronic isotope shifts are derived

$\text{ΔE}{}_{\mathrm{e}}{}^{\mathrm{i}}\text{(}\text{BeH}\text{?}\text{BeT}\text{) = ?4.7 ≠ 1.5}\text{cm}{}^1\text{, ΔE}{}_{\mathrm{e}}{}^{\mathrm{i}}\text{(}\text{BeH}\text{?}\text{BeT}\text{) = ?1.8 ≠ 1.5}\text{cm}{}^1$

and related to the theoretical approach given by Bunker to the problem of the breakdown of the Born-Oppenheimer approximation.     

Ar+ laser-induced fluorescence spectra of Cs2: The E1Σu+ and (1) 1Πg electronic states

Laser-induced fluorescence of Cs₂ molecules in the infrared (1.15–2.5 μm) and the visible (505–545 nm) regions has been observed using several excitation wavelengths from an argonion laser. Accurate molecular constants and potential energy curves for the pumped E¹Σ_u⁺ state and the first excited gerade ¹Π state are derived from more than 1300 fluorescence lines precisely measured with a high-resolution Fourier transform interferometer. The main molecular constants for the states are

The A2Π-X2Π system of the SbO molecule

The emission spectrum of the A²Π-X²Π system of the SbO molecule has been photographed under high resolution, and the rotational structure in eight bands of the ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ component, involving v′ = 0–2 and v″ = 1–4, has been analyzed for both isotopic molecules ¹²¹SbO and ¹²³SbO. The observed rotational lines of the corresponding ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ component are broad, with a width of about 0.2 cm^?1 varying little with J. It is suggested that these broad lines represent unresolved components arising from magnetic hyperfine interaction with ¹²¹Sb or ¹²³Sb nuclei. Isotopic shift observations contradict earlier vibrational assignments in the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ subsystem and indicate that the A state is inverted in agreement with expectations from related systems. The principal molecular constants (in cm^?1) obtained for ¹²¹SbO are

High resolution Fourier spectroscopy of P2 infrared emission spectrum: Analysis of two new systems b3Πg → w3Δu and A1Πg → W1Δu

The investigation of the emission infrared spectrum of P₂ was performed with a high resolution Fourier spectrometer. Two new electronic systems were attributed to b³Π_g → w³Δ_u and A¹Π_g → W¹Δ_u transitions. The molecular parameters are obtained by a complete fitting procedure. The main equilibrium constants of the new states are (in cm^?1):

$\text{ω}{}^3\text{Δ}{}_{\mathrm{u}}\text{T}{}_{\mathrm{e}}\text{= 243228.07 ω}{}_{\mathrm{e}}\text{= 591.3 ω}{}_{\mathrm{e}}\text{X}{}_{\mathrm{e}}\text{= 2.5}$

$\text{B}{}_{\mathrm{e}}\text{= 0.256040 δ}{}_{\mathrm{e}}\text{= 0.001409 D}{}_{\mathrm{e}}\text{= 19.0 X 10}{}^{\mathrm{?8}}$

$\text{W}{}^1\text{Δ}{}_{\mathrm{u}}\text{T}{}_{\mathrm{e}}\text{= 31096.64 W}{}_{\mathrm{e}}\text{= 627.206 W}{}_{\mathrm{e}}\text{X}{}_{\mathrm{e}}\text{= 2.331}$

$\text{B}{}_{\mathrm{e}}\text{= 0.2628 δ}{}_{\mathrm{e}}\text{= 0.0014 D}{}_{\mathrm{e}}\text{= 23 X 10}{}^{\mathrm{?8}}$

     

High-resolution laser excitation spectroscopy: Analysis of the B2Σ+-X2Σ+ system of CaCl

Single-mode cw dye laser excitation spectra of the (0, 0), (1, 1), and (2, 2) bands of the B²Σ⁺-X²Σ⁺ system of CaCl have been observed and assigned. Some 300 independent photo-luminescence spectra have been used in making the rotational assignment and demonstrate the power of the technique of line-by-line analysis in unraveling complex spectra. Spectroscopic constants (cm^?1) obtained from a weighted least squares fit of the data are given below. Numbers in parentheses refer to 95% confidence limits in the last digit.

Vibration-rotation and deperturbation analysis of A2Π-X2Σ+ and B2Σ+-X2Σ+ systems of the CaI molecule

Doppler-limited laser excitation spectroscopy employing narrow-band fluorescence detection was used to obtain a rotational and vibrational analysis in the (0, 0) and (1, 1) bands of the A²Π-X²Σ⁺ system and the (4, 2) (3, 1), (0, 0), (0, 1), (1, 2), (2, 3), and (3, 4) bands of the B²Σ⁺-X²Σ⁺ system of CaI. The A and B states are deperturbed to obtain spectroscopic constants and Franck-Condon factors. Deperturbation was necessary because of the small separation of the A and B states relative to the A ～ B interaction strength and the A²Π spin-orbit splitting. The main deperturbed constants (in cm^?1) are

The A3Π-X0+, 1 band system of the SeO molecule

A new weak emission band system of the SeO molecule consisting of 34 band heads degraded to shorter wavelengths has been observed for the first time in the spectral region 6730–8570 Å. The vibrational analysis of the system suggests that it arises from the transition A³Π_reg-X0⁺, 1. All the five subsystems allowed by the selection rule $\text{ΔΩ}\text{= 0}$, ±1 have been identified. The constants in cm^?1 derived for the A³Π state are