Ne-HCN Millimeter-wave spectroscopy of the internal rotation bands of the Ne-HCN complex

IntroductionNeqRNCHDe = 63 cm-1Gutowski et al. 1993FTMW J = 1-03-2Toczylowski et al. 2001CCSD(T) V(R,q) Potential Energy Surface V(R,q)

0100200300 j = 0 j = 2 j = 1E(GHz)S2D2P1P2S1S01331060310280300|K|021

1080Hz165192 GHzTrot = 2 KWhite

170180190Frequency / GHzD2-P1P2-P1P2-S1S2-P1S2-S1

P2-S161Q(J)72P(J)D2S1P1P2S2170180190Frequency / GHze, fe, f

D2-P1D2S1P1P2S2170180190Frequency / GHz2Q(J) e-f25Q(J) f-e61R(J) f-f461R(J) e-ee, fe, f

3 32 11 2D2-P1Q(2) e-fF = 2 21 13 22 3Obs.Calc.1654303327Frequency / MHz14N (I = 1) eQqJD2e (J = 2) 0.8160 MHzP1f (J = 2) -0.9270 MHz

300400500S 2D 2P 2efef0717172727 j = 2E(GHz)12JJJ

Data (j = 10 35 lines, j = 21 46 lines) 254 kHz V(R, q) = Vab initio (R,q) S fm Pm(cosq) R = R S gm Pm(cosq)PES V(R,q)Hamiltonianfm 6gm 6HCN

Potential Energy SurfaceRqMinimumEnergy Path(MEP)De = 62.9 cm-1Ne HCNHCN Ne090180

MEP-60-50-40V-30cm-1ab initioexp.()Ground State (S0)S1S2P2P1D2090180qNe HCNNe NCHj = 1j = 2j = 0

Ne-HCNNe HCNHCN Ne3456090180090180090180 = 3.973 = 105.74 = 3.905 = 82.63 = 3.727 = 83.88 MEP

S2()

S0()-6-4-20246-6-4-20246

q = 0010-10-20-30-40-50-6045678Vcm-1R / S1S2S3nSS4nSS1S5K = 0S0

MEP045901351800-20-40-60-80-100-120-140-160Vcm-1Rg HCNHCN Rg

Ne-HCN D2-P1P2-P1S2-P1P2-S1S2-S1j = 1-0 j = 2-1Potential Energy Surface

0-10-20-30-40E (cm-1)Ground state(S0)14Str.3Str.+11323SPD

Potential Parameterf00.998906(46) f1-0.109238(12)f2-0.011507(14)f3 -0.034717(26)f40.024482(26)f5 0.014898(40)

g01.0004936(15)g1-0.0108596(19)g2-0.0020830(30)g3-0.0013153(52)g40.002865(18)g50.001876(29)Ne-HCNV(R, q) = VCCSD(T)(R,q) S fm Pm(cosq) R = R S gm Pm(cosq)

170180190Frequency / GHzD2-P1P2-P1P2-S1S2-P1S2-S1

170180190Frequency / GHz

S2-S1170180190Frequency / GHz16R(J)

S2-P1170180190Frequency / GHz51Q(J) 43P(J)

P2-P1170180190Frequency / GHz74P(J) f-f

01234567300400500P2fS2D2eP2eD2fJE(GHz) j = 2

Average Structure of Ne-HCN 3.970 1/252.88degunitS0Ne-HCN 3.921 1/280.45degS1 3.766 1/277.62degP1

Average Structure of Ne-HCN 3.973 105.74degunitS2Ne-HCN 3.905 82.63degP2 3.727 83.88degD2

Ne-HCNS0 state J = 0Rq

Ne-HCNS1 state J = 0Rq

Ne-HCNP1 state J = 1Rq

P2()

D2()

DCN0.5%He,DCN2040Hz18inch diffusion pump2x10^-4 torr136146GHz10InSbj = 113j =21DCNbDCNfixab initiofm,gm4.6MHzfm4gmHe-DCNHe-HCN