1. Analysis of interactions between excited vibrational states in the FASSST rotational spectrum of S(CN) 2 Zbigniew Kisiel, Orest Dorosh Institute of Physics, Polish Academy of Sciences Ivan R. Medvedev, Marcus Behnke, Manfred Winnewisser, Frank C. De Lucia, Eric Herbst, Department of Physics, The Ohio State University 61st OSU International Symposium on Molecular Spectroscopy TH09

2. The challenge: The solution: FASSST mmw spectrum (see WI04) continuous 110.1 – 374.3 GHz spectrum recorded at OSU at frequency accuracy of ca 50 kHz, resolution of 0.5-1 MHz, and containing >100000 measurable lines Computer packages for efficient data reduction = CAAARSAABS CAAARS (WI04) and AABS http://info.ifpan.edu.pl/~kisiel/prospe.htmhttp://info.ifpan.edu.pl/~kisiel/prospe.htm

3. Synchronized cursors and frequency axes Name of data file for the fitting program Quantum numbers of the current transition (up to six per energy level) Predictions for many spectroscopic species can be displayed simultaneously and differentiated with various color, linestyle and highlighting SVIEW_L = spectral viewer ASCP_L = viewer of predictions Indicator of transition already in the fitting dataset Name of predictions file containing the current transition Indicator of synchronized operation when a single keystroke actions measurement of line closest to prediction and adds the frequency and quantum numbers to the dataset

4. Synthetic overview of the ground state dataset Symbol size is proportional to: ( obs - calc )/  Red symbols denote ( obs - calc ) > 3 

5. Lowest energy vibrational states in S(CN) 2  4 = 122 cm - 1 A 1  7 = 328  8 = 366  9 = 372  3 = 496 Frequencies are unscaled B3LYP/6-31G(d,p) Other modes (cm - 1 ): obs.calc.  2 672 685A 1 6 690 688B 1 5 21802293B 1 1 23082308A 1 B1B1 B2B2 A2A2 A1A1

6. Loomis-Wood plot centered on K a = 1 - 0 transitions in the ground state  8 = 1  7 = 1  9 = 1 gs = 2= 3  4 = 1

7.  4 = 3  9 = 1, K a =1 - 0 K a =2 - 1 K a =3 - 2

8. Perturbations between and visible in R-type transitions Perturbations between  8 = 1 and  9 = 1 visible in R-type transitions

9. Perturbations  and  Perturbations (  8 = 1   9 = 1) and (  8 = 1   4 = 3) R-type Q-type

10.  4 = 3 A 1  8 = 1 B 2  9 = 1 A 2 A 1  B 2 = B 2 R a :  E + F bc +… (4 constants) A 2  B 2 = B 1 R c :  E + F ab +… (8 constants)  (c) = 0 ! A 1  A 2 = A 2 R b : F ac +… (3 constants) H cor = i(G  +…)P  + (F  +…) (P  P  +P  P  )…

11. Plots of (1-p mix ) for energy levels in the interacting triad near 370 cm - 1

12. Plots of obs-calc differences for measured rotational transitions in the 370 cm - 1 triad

13.  4 = 4 A 1  8 = 1  4 = 1 B 2  9 = 1  4 = 1 A 2 A 1  B 2 = B 2 R a :  E + F bc +… (4 constants) A 2  B 2 = B 1 R c :  E + F ab +… (8 constants) A 1  A 2 = A 2 R b : F ac +… (3 constants)  3 = 1 A 1 A 1  A 1 = A 1 W 14 +… (3 constants) A 1  A 2 = A 2 R b : F ac +… (3 constants) B 2  A 1 = B 2 R a :  E + F bc +… (4 constants)

14. (1-p mix ) plots for the interacting tetrad of states near 500 cm - 1

15. Obs-calc plots for the interacting tetrad of states near 500 cm - 1

17. Assignment of vibrational satellites (using relative intensity, statistical weights and inertial defects):  calc  weightInertial defect (uA 2 ) (cm - 1 ) obs. calc. gs 0.49041(1) 0.480 4 122 A 1 + 1.38528(2) 1.370 7 323 B 1 -- 0.79070(3) - 0.852 8 366 B 2 - 0.71380(3) 0.688 9 372 A 2 + 1.00655(3) 1.131 3 496 A 1 + 0.95354(5) 0.947  calc  weightInertial defect (uA 2 ) (cm - 1 ) obs. calc. gs 0.49041(1) 0.480 4 122 A 1 + 1.38528(2) 1.370 7 323 B 1 -- 0.79070(3) - 0.852 8 366 B 2 - 0.71380(3) 0.688 9 372 A 2 + 1.00655(3) 1.131 3 496 A 1 + 0.95354(5) 0.947 Weight denotes statistical weights relative to the ground state: + stands for unchanged - denotes reversed weights Calc results from uscaled B3LYP/6-31G(d,p) ReassignedReassigned

18. Vibrational energy differences resulting from coupled fits tetrad near 500 cm - 1 : triad near 370 cm - 1 :

19. Conclusions:Conclusions: FASSST spectrum of S(CN) 2 assigned, over 18000 lines measured and analysed resulting in: Precise constants for the ground state and all 11 different vibrational excited states of the parent isotopomer for vibrational energy up to ca 500 cm - 1 Constants for ground states of 34 S and 13 C isotopomers Deviations of fits from 50 to 100 kHz Confident assignment of first excited states of five different normal modes Many precise vibrational energy level differences + … AABS Creation of highly efficient AABS software package in order to manage data for many states simultaneously

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