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B(1)1Π state of KCs: High-resolution spectroscopy and description of low-lying energy levels
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10.1063/1.3683218
/content/aip/journal/jcp/136/6/10.1063/1.3683218
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/6/10.1063/1.3683218

Figures

Image of FIG. 1.
FIG. 1.

Scheme of potential energy curves of the low-lying electronic states of the KCs molecule based on Hund's case “a” calculations in Ref. 7 (upper graph) and Hund's case “c” calculations in Ref. 8 (lower graph, where the letters at potentials are referring to the “a” case).

Image of FIG. 2.
FIG. 2.

KCs LIF spectrum excited by laser frequency 14 090.268 cm−1 and recorded with a silicon detector. The spectrum contains only BX transitions. The dominant progression originates from the v = 3, J = 129 level of the B(1)1Π state (line positions are marked below the spectrum). No spin-forbidden transitions to the a 3Σ+ state are observed.

Image of FIG. 3.
FIG. 3.

KCs LIF spectrum excited by laser frequency 14 176.394 cm−1 and recorded with a silicon detector. The spectrum contains both spin-allowed BX and spin-forbidden Ba transitions. The dominant KCs LIF progressions to the singlet and triplet states originate from the v = 4, J = 88 level of B(1)1Π state (line positions are marked with vertical lines below the spectrum). LIF lines close to exciting laser are weakened by a long-pass filter. The inset contains the Ba bands.

Image of FIG. 4.
FIG. 4.

An example of the LIF intensity distribution over v ′′ in the BX bands. (a) the LIF progression is excited at a laser frequency of 13 712.700 cm−1, assigned to the R-transition B(0, 119) ← X(4, 118). (b) the LIF progression is excited at a laser frequency of 14 071.926 cm−1, assigned to the Q-transition B(1, 51) ← X(0, 51).

Image of FIG. 5.
FIG. 5.

An expanded example of rotational relaxation from the spectrum shown in Fig. 2. The portion of the spectrum presented corresponds to the B(3, 129) → X(12, 129) transition (most intense line). Q-, P-, and R-lines are marked by bars below the spectrum.

Image of FIG. 6.
FIG. 6.

J -dependence of experimental term values in the reduced energy scale E red = E − 0.02J (J + 1). Short arrows mark levels (0, 119) and (1, 51) producing the LIF intensity distributions shown in Fig. 4. Insets show term value plots of another state (most likely C(3)1Σ+) crossing the plots of B(1)1Π state at (2, 95) and (5, 144). v -numbering from 0 to 8 is indicated. Enlarged symbols (×) and red dotted lines represent term values of the C-state. The lowest v* term is constructed basing on perturbation centers at v = 0, J = 108 and v = 1, J = 63.

Image of FIG. 7.
FIG. 7.

J -dependence of (a) the Λ-doubling constant q(v ) and (b) the rotational constant for v = 0.

Image of FIG. 8.
FIG. 8.

J -dependence of the differences between measured term values and their counterparts calculated using the data from Tables I and II. Horizontal lines indicate experimental uncertainty ±0.01 cm−1. Arrow marks the level (2, 94).

Image of FIG. 9.
FIG. 9.

(a) Example of BX LIF spectra exhibiting weak LIF lines around 11 280 cm−1. LIF progressions from directly excited B 1Π(v = 2, J = 94) level is marked by vertical bars below the spectrum; the inset expands the rotational relaxation pattern for v ′′ = 9 from the directly excited B 1Π(v = 2, J = 94) level. (b) Enlarged fragment of the spectrum around v ′′ = 50 and 51. LIF from directly excited level is marked by red vertical bars below the spectrum, collision-induced LIF from a state with J = 94 is marked by blue dots above the spectrum. LIF from a directly excited C-state level is marked by an asterisk.

Image of FIG. 10.
FIG. 10.

(a) v ′′-dependence of the relative intensities of C 1Σ+X 1Σ+ LIF. Red shaded bars represent the experiment, black bars are FCFs calculated using the C 1Σ+ PEC from Ref. 7; the data are matched at v ′′ = 50. (b) ΔG v dependence on the energy of the respective levels. Dots represent the experiment, lines are calculated from ab initio PECs (Refs. 6 and 7) (solid lines – for C 1Σ+, dotted lines – for c 3Σ+).

Tables

Generic image for table
Table I.

List of the grid points of the IPA potential for the KCs B(1)1Π state. Energies are given with respect to the minimum of the ground state.

Generic image for table
Table II.

The q 0 and q 1 values (in cm−1) fitted for the four lowest vibrational levels of the B(1)1Π state.

Generic image for table
Table III.

Comparison of experimental E expt and calculated (by pointwise PEC) rovibronic term values E calc for the 41K133Cs isotopologue of the B(1)1Π state. All energies are in cm−1.

Generic image for table
Table IV.

Dunham coefficients Y ij obtained by fitting the data for v ∈ [0, 3], J ∈ [7, 233] of the B(1)1Π state of 39K133Cs. All values are in cm−1.

Generic image for table
Table V.

Molecular constants for particular v -levels of the B(1)1Π state of 39K133Cs. All values are in cm−1.

Generic image for table
Table VI.

Molecular constants of the B(1)1Π state of 39K133Cs fitted in the present work compared with their ab initio counterparts. T e and ω e in cm−1, R e in Å.

Generic image for table
Table VII.

Tentative molecular constants for the C-state, all values in cm−1. v* (see Fig. 6) is estimated as 18 ± 2 by comparing experimental intensity distribution (see Fig. 9(a)) and term values with calculations basing on Ref. 7.

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/content/aip/journal/jcp/136/6/10.1063/1.3683218
2012-02-13
2014-04-23
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: B(1)1Π state of KCs: High-resolution spectroscopy and description of low-lying energy levels
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/6/10.1063/1.3683218
10.1063/1.3683218
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