1. GEORG MELLAU1,2 and ROBERT FIELD2
Correlation between the shape and the excitation of the angular momentum for the HCN/HNC molecule
GEORG MELLAU1,2 and ROBERT FIELD2
1) Physikalisch-Chemisches Institut, Justus Liebig Universität Giessen, Giessen, Germany
2) Department of Chemistry, MIT, Cambridge, MA, USA
Urbana,

2. Internal structure of molecules
H. Primas, Chemie in unserer Zeit, 19, 109 (1985), G. Ch. Mellau, in preparation

3. Isomerisation as bond-breaking “vibration”
Simulation : B. Eifert and G. Ch. Mellau, Potential function form: Mourik et al. J. Chem. Phys., 2001, 115,

4. Absorption ↔ Emission HCN, absorption, 200m, 2mbar
HCN, emission, 2mbar, 1100 C
Transmittance
Wavenumber /cm-1
FTIR Hot gas infrared emission (HOTGAME) spectra are extremely rich in transitions in comparison with even very long path absorption measurements (G. Mellau and M. Winnewissser , 1997)

5. Eigenstates ↔ potential energy surface
eigenstates
G.Ch. Mellau, J. Chem. Phys. 133, (2010), G.Ch. Mellau, J. Chem. Phys.,134, (2011),
T. Furtenbacher, P. Arendas, G. Mellau and A. G. Csaszcar, Simple molecules as complex systems, Sci. Rep., 4, (2014)

6. Ab initio [H,C,N] eigenenergies: v1v2lv3 ?
e, J=0
0.0000 …
e, J=1
2.9100
f, J= … … … … … … … … … … … …
e, J=60
f, J=60
0000
0110
0200
0220
Complete assignment of all ab initio rotation-vibration eigenenergies up to cm-1 above the minimum of the potential energy surface including all rovibrational states below and 1500 cm-1 above the isomerization barrier

7. Vibrations: The onset of isomerization v2≥22
G.Ch. Mellau . J. Chem. Phys., 134, (2011)

8. Visualization of the HCN rotational eigenenergies
-Ev,J=0
0000
E0,J
01800 E
Er= E - Ev,J=0 - E0,J E
Ev,J=0 J

9. The shape from „energetic spincurve”
The molecule is rotating faster and faster
Er= E - Ev,J=0 - E0,J
Er /cm-1
01800 +
B↑ Imech↓ - J
B ↓ Imech↑
0007

10. v2l : Vibrational angular momentum

11. v2l : Vibrational angular momentum

12. HCN states with highest l-excitation
The molecule is rotating faster and faster + l
G. Ch. Mellau J. Chem. Phys., 134, (2011), G.Ch. Mellau J. Chem. Phys., 134, (2011)

13. HCN states with highest l-excitation (ab initio)
The molecule is rotating faster and faster + -
B ↓ Imech↑ l
0000 ~
G. Ch. Mellau J. Chem. Phys., 134, (2011), G.Ch. Mellau J. Chem. Phys., 134, (2011)

14. Experimental HCN states with high l-excitation

15. High l states of HNC
G.Ch. Mellau . J. Chem. Phys., 134, (2011)

16. HCN/HNC high l nν1+mν2 states (ab initio)

17. HCN/HNC high l nν3+mν2 states v (ab initio)

18. HCN/HNC high l nν3+mν2 states (ab initio)

19. High l states of DCN pure bending states66 55
1111 44
T - Tv,J=0 - T0,J 33 22 11 J
Mölleman et all . J. Mol. Spectr., 212, (2002)

20. H-CN vs. HN-C bond

21. Hot H2O and isotopologues
Acknowledgments
Hot H13CN, HC15N, H13 C15N, D 13 C15N
Universität Leipzig
Wolfgang Quapp
Washington, USA
Art Maki
Hot HC15N
University of Lethbridge
Lethbridge, Canada
Adriana Predoi-Cross
Hot H13CN
Bianca Eifert, Jan Philipp Hofmann
Hot H2O and isotopologues
Université de Reims,
Reims, France
Vladimir Tyuterev
Institute of Atmospheric
Optics, Tomsk, Russia
Semen Mikhailenko
E. Starikova
Eötvös University,
Budapest, Hungary
Attila Császár
Hot CO2
Valery Perevalov
Yurii Borkov
Prof. Robert Field
HCN/HNC line and band intensities from absorption and emission spectra
Justus-Liebig-Universität Gießen
Jan Schostag
HCN/HNC model systems
Kai Exner

22. The End of the Story

23. Effective frequency plot - l=0 bending states
11546(48) cm-1
16649(95) cm-1
16649 cm-1
11517 cm-1

24. Effective frequency plot - l=1 bending states
11558(210) cm-1
16780(106) cm-1
16649 cm-1
11517 cm-1

25. Effective frequency plot - l=2 bending states
11498(205) cm-1
16568(17) cm-1
16649 cm-1
11517 cm-1

26. Effective frequency plot - l=3 bending states
11555(178) cm-1
16885(2) cm-1
16649 cm-1
11517 cm-1

27. Effective frequency plot – l>3… bending states1% …