Rotational, Centrifugal Distortion, Internal Rotation Calculation (V2.5e) Holger Hartwig 08-Nov-96 (hartwig@phc.uni-kiel.de) Please cite: H.Hartwig and H.Dreizler, Z.Naturforsch, 51a (1996) 923. Calculation date and time: Type help now for the list of parameters : Acetaldehyde, Maes,Wlodarczak,Boucher,Demaison Z.Naturforsch. 42a,97(1987) nzyk 100 print 4 eval 0 dfreq 0 orger 0 ints 0 maxm 8 woods 33 ndata 0 nfold 3 spin 0 ntop 1 adjf 0 maxvm 0 aprint 75 xprint 20 ncycl 100 svderr 0 fitscl 0 reduct 0 rofit .0000000D+00 eps .1000000D-11 defer .1000000D-04 weigf .0000000D+00 convg .9990000D+00 lambda .1000000D-04 freq_l .6000000D+01 freq_h .1800000D+02 limit .1000000D+00 temp .2000000D+01 Using Watson A Reduction assumed sizeb 1 \\ set (adj or 16) \\ set (adj or 8) \\ set (adj or 1) \\ adj 1: adjust F according to rho, beta and gamma \\ adj 8: adjust rho according to F0 = 1/(2 I_alpha) \\ adj 16: adjust beta and gamma according delta + epsil new adj : 25 BJ 1.189419650 BK 3.813470350 B- .135110250 DJ 1.971000E-6 DJK -14.210000E-6 dj -.821316E-6 mu_y 1.000000000 mu_z 5.500000000 F 161.157365267 V1n 5468.440000 rho .023171458 beta 2.882775552 F0 157.929000000 delta 2.356190000 fit .1D+00 .1D+01 BJ 1.00 fit .1D+00 .1D+01 BK 1.00 fit .1D+00 .1D+01 B- 1.00 fit .1D+00 .1D+01 DJ 1.00 fit .1D+00 .1D+01 DJK 1.00 fit .1D+00 .1D+01 dj 1.00 dqx .1D+00 .1D+01 V1n_1 1.00 dqx .1D+00 .1D+01 delta_1 1.00 /A S 0 /E S 1 V 0 ndata 38 Data Points 38 Splittings 0 Effective Data Points 1.5 \\ Maximal K = J = 8 \\ B= 1 adj= 25 \\ (1) calculate torsional integrals \\ (32)use torsional integrals in rigid rotor H_rr Sigma: .339045D-02 Sigma/OldSigma: .000000 conv: 1 J K- K+ J K- K+ Sym calc/GHz diff/MHz obs/GHz 1: 3 1 2 2 1 1 /A 7.5341410 -1.7170 7.5324240 Err .5D-04 /A -/A 2: 4 1 4 3 1 3 /A 8.9476936 -.2926 8.9474010 Err .5D-04 /A -/A 3: 4 0 4 3 0 3 /A 9.3749298 -1.0948 9.3738350 Err .5D-04 /A -/A 4: 4 1 3 3 1 2 /A 10.0274769 -2.4109 10.0250660 Err .5D-04 /A -/A 5: 5 1 5 4 1 4 /A 11.1602458 -.0058 11.1602400 Err .5D-04 /A -/A 6: 5 0 5 4 0 4 /A 11.6189642 -.9832 11.6179810 Err .5D-04 /A -/A 7: 5 2 4 4 2 3 /A 11.8636034 -1.6774 11.8619260 Err .5D-04 /A -/A 8: 5 2 3 4 2 2 /A 12.1395107 -2.4627 12.1370480 Err .5D-04 /A -/A 9: 5 1 4 4 1 3 /A 12.5038670 -3.1740 12.5006930 Err .5D-04 /A -/A 10: 6 0 6 5 0 5 /A 13.8095044 -.4944 13.8090100 Err .5D-04 /A -/A 11: 6 3 4 5 3 3 /A 14.3413046 -2.3416 14.3389630 Err .5D-04 /A -/A 12: 6 2 4 5 2 3 /A 14.6730215 -3.5155 14.6695060 Err .5D-04 /A -/A 13: 6 1 5 5 1 4 /A 14.9572301 -3.9701 14.9532600 Err .5D-04 /A -/A 14: 7 1 7 6 1 6 /A 15.5430447 1.4713 15.5445160 Err .5D-04 /A -/A 15: 7 0 7 6 0 6 /A 15.9521362 .4868 15.9526230 Err .5D-04 /A -/A 16: 7 2 5 6 2 4 /A 17.2390233 -4.9313 17.2340920 Err .5D-04 /A -/A 17: 7 1 6 6 1 5 /A 17.3803627 -4.7207 17.3756420 Err .5D-04 /A -/A 18: 8 1 8 7 1 7 /A 17.7128102 2.8248 17.7156350 Err .5D-04 /A -/A 19: 8 0 8 7 0 7 /A 18.0592786 2.0274 18.0613060 Err .5D-04 /A -/A 20: 3 K 1 2 K 1 /E 7.5122266 -3.1066 7.5091200 Err .5D-04 /E -/E 21: 4 K -1 3 K -1 /E 8.9549818 .5532 8.9555350 Err .5D-04 /E -/E 22: 4 K 0 3 K 0 /E 9.3719707 -.9717 9.3709990 Err .5D-04 /E -/E 23: 4 K 1 3 K 1 /E 10.0160487 -2.9367 10.0131120 Err .5D-04 /E -/E 24: 5 K -1 4 K -1 /E 11.1630362 .5068 11.1635430 Err .5D-04 /E -/E 25: 5 K 0 4 K 0 /E 11.6160716 -.8766 11.6151950 Err .5D-04 /E -/E 26: 5 K -2 4 K -2 /E 11.9441781 .4049 11.9445830 Err .5D-04 /E -/E 27: 5 K 2 4 K 2 /E 12.0540627 -3.9897 12.0500730 Err .5D-04 /E -/E 28: 5 K 1 4 K 1 /E 12.4952499 -3.2409 12.4920090 Err .5D-04 /E -/E 29: 6 K 0 5 K 0 /E 13.8068212 -.4416 13.8063796 Err .5D-04 /E -/E 30: 6 K -3 5 K -3 /E 14.3525885 -2.1325 14.3504560 Err .5D-04 /E -/E 31: 6 K 2 5 K 2 /E 14.5941036 -6.5656 14.5875380 Err .5D-04 /E -/E 32: 6 K 1 5 K 1 /E 14.9489913 -3.8433 14.9451480 Err .5D-04 /E -/E 33: 7 K -1 6 K -1 /E 15.5427150 1.8040 15.5445190 Err .5D-04 /E -/E 34: 7 K 0 6 K 0 /E 15.9496771 .5289 15.9502060 Err .5D-04 /E -/E 35: 7 K 2 6 K 2 /E 17.1852566 -7.8226 17.1774340 Err .5D-04 /E -/E 36: 7 K 1 6 K 1 /E 17.3717840 -4.4940 17.3672900 Err .5D-04 /E -/E 37: 8 K -1 7 K -1 /E 17.7118704 3.0876 17.7149580 Err .5D-04 /E -/E 38: 8 K 0 7 K 0 /E 18.0569934 2.0596 18.0590530 Err .5D-04 /E -/E Maximum (obs-calc)/err in line 35 .0078226 indep.par: 8 stepw:1.0000 lambda: .400D-05 cond.no: .218D+03 ------------------------------------------------------- Iteration : 1 Sigma: .691536D-04 Sigma/OldSigma: .020397 conv: 1 Parameters Change BJ 1.189257494 { -.000162156} BK 3.807913341 { -.005557009} B- .134952521 { -.000157729} DJ 1.983107E-6 { .012107E-6} DJK -14.182158E-6 { .027842E-6} dj .715419E-6 { 1.536735E-6} mu_y 1.000000000 { fixed } mu_z 5.500000000 { fixed } F 161.294561110 { derived} V1n 5469.263360 { .823360} rho .023872215 { derived} beta 2.900168928 { derived} F0 157.929000000 { fixed } delta 2.392885881 { .036695881} dj (1) .715419E-6 1.536735E-6 214.802% Max. Change indep.par: 8 stepw:1.0000 lambda: .160D-05 cond.no: .220D+03 ------------------------------------------------------- Iteration : 2 Sigma: .363852D-04 Sigma/OldSigma: .526151 conv: 1 Parameters Change BJ 1.189257694 { .000000200} BK 3.807933718 { .000020377} B- .134954640 { .000002119} DJ 1.979711E-6 { -.003396E-6} DJK -14.138339E-6 { .043819E-6} dj .721189E-6 { .005770E-6} mu_y 1.000000000 { fixed } mu_z 5.500000000 { fixed } F 161.298759800 { derived} V1n 5467.194615 { -2.068745} rho .023893604 { derived} beta 2.900679100 { derived} F0 157.929000000 { fixed } delta 2.393981513 { .001095632} dj (1) .721189E-6 .005770E-6 .800% Max. Change indep.par: 8 stepw:1.0000 lambda: .640D-06 cond.no: .220D+03 ------------------------------------------------------- Iteration : 3 Sigma: .363850D-04 Sigma/OldSigma: .999993 conv: 2 Parameters Change BJ 1.189257695 { .000000001} BK 3.807933759 { .000000041} B- .134954646 { .000000007} DJ 1.979704E-6 { -.000007E-6} DJK -14.138200E-6 { .000139E-6} dj .721210E-6 { .000021E-6} mu_y 1.000000000 { fixed } mu_z 5.500000000 { fixed } F 161.298759968 { derived} V1n 5467.202747 { .008132} rho .023893605 { derived} beta 2.900679117 { derived} F0 157.929000000 { fixed } delta 2.393981550 { .000000037} dj (1) .721210E-6 .000021E-6 .003% Max. Change indep.par: 8 stepw:1.0000 lambda: .256D-06 cond.no: .220D+03 ------------------------------------------------------- Iteration : 4 Sigma: .363850D-04 Sigma/OldSigma:1.000000 conv: 3 dj (1) .721210E-6 .000000E-6 .000% Max. Change indep.par: 8 stepw:1.0000 lambda: .256D-06 cond.no: .220D+03 Recalculation of the spectrum ######################################################### End at Cycle 4 J K- K+ J K- K+ Sym calc/GHz diff/MHz obs/GHz 1: 3 1 2 2 1 1 /A 7.5324338 -.0098 7.5324240 Err .5D-04 /A -/A 2: 4 1 4 3 1 3 /A 8.9474228 -.0218 8.9474010 Err .5D-04 /A -/A 3: 4 0 4 3 0 3 /A 9.3738459 -.0109 9.3738350 Err .5D-04 /A -/A 4: 4 1 3 3 1 2 /A 10.0250723 -.0063 10.0250660 Err .5D-04 /A -/A 5: 5 1 5 4 1 4 /A 11.1602690 -.0290 11.1602400 Err .5D-04 /A -/A 6: 5 0 5 4 0 4 /A 11.6179908 -.0098 11.6179810 Err .5D-04 /A -/A 7: 5 2 4 4 2 3 /A 11.8619347 -.0087 11.8619260 Err .5D-04 /A -/A 8: 5 2 3 4 2 2 /A 12.1370644 -.0164 12.1370480 Err .5D-04 /A -/A 9: 5 1 4 4 1 3 /A 12.5006920 .0010 12.5006930 Err .5D-04 /A -/A 10: 6 0 6 5 0 5 /A 13.8090219 -.0119 13.8090100 Err .5D-04 /A -/A 11: 6 3 4 5 3 3 /A 14.3389579 .0051 14.3389630 Err .5D-04 /A -/A 12: 6 2 4 5 2 3 /A 14.6695165 -.0105 14.6695060 Err .5D-04 /A -/A 13: 6 1 5 5 1 4 /A 14.9532462 .0138 14.9532600 Err .5D-04 /A -/A 14: 7 1 7 6 1 6 /A 15.5445680 -.0520 15.5445160 Err .5D-04 /A -/A 15: 7 0 7 6 0 6 /A 15.9526423 -.0193 15.9526230 Err .5D-04 /A -/A 16: 7 2 5 6 2 4 /A 17.2340873 .0047 17.2340920 Err .5D-04 /A -/A 17: 7 1 6 6 1 5 /A 17.3756103 .0317 17.3756420 Err .5D-04 /A -/A 18: 8 1 8 7 1 7 /A 17.7157063 -.0713 17.7156350 Err .5D-04 /A -/A 19: 8 0 8 7 0 7 /A 18.0613428 -.0368 18.0613060 Err .5D-04 /A -/A 20: 3 K 1 2 K 1 /E 7.5090932 .0268 7.5091200 Err .5D-04 /E -/E 21: 4 K -1 3 K -1 /E 8.9554982 .0368 8.9555350 Err .5D-04 /E -/E 22: 4 K 0 3 K 0 /E 9.3710408 -.0418 9.3709990 Err .5D-04 /E -/E 23: 4 K 1 3 K 1 /E 10.0131381 -.0261 10.0131120 Err .5D-04 /E -/E 24: 5 K -1 4 K -1 /E 11.1635127 .0303 11.1635430 Err .5D-04 /E -/E 25: 5 K 0 4 K 0 /E 11.6152043 -.0093 11.6151950 Err .5D-04 /E -/E 26: 5 K -2 4 K -2 /E 11.9445236 .0594 11.9445830 Err .5D-04 /E -/E 27: 5 K 2 4 K 2 /E 12.0500376 .0354 12.0500730 Err .5D-04 /E -/E 28: 5 K 1 4 K 1 /E 12.4919988 .0102 12.4920090 Err .5D-04 /E -/E 29: 6 K 0 5 K 0 /E 13.8063792 .0004 13.8063796 Err .5D-04 /E -/E 30: 6 K -3 5 K -3 /E 14.3504913 -.0353 14.3504560 Err .5D-04 /E -/E 31: 6 K 2 5 K 2 /E 14.5875088 .0292 14.5875380 Err .5D-04 /E -/E 32: 6 K 1 5 K 1 /E 14.9451682 -.0202 14.9451480 Err .5D-04 /E -/E 33: 7 K -1 6 K -1 /E 15.5444531 .0659 15.5445190 Err .5D-04 /E -/E 34: 7 K 0 6 K 0 /E 15.9501611 .0449 15.9502060 Err .5D-04 /E -/E 35: 7 K 2 6 K 2 /E 17.1774430 -.0090 17.1774340 Err .5D-04 /E -/E 36: 7 K 1 6 K 1 /E 17.3673259 -.0359 17.3672900 Err .5D-04 /E -/E 37: 8 K -1 7 K -1 /E 17.7149274 .0306 17.7149580 Err .5D-04 /E -/E 38: 8 K 0 7 K 0 /E 18.0589913 .0617 18.0590530 Err .5D-04 /E -/E Maximum (obs-calc)/err in line 18 .0000713 RMS deviations (MHz), B and V sorted B V n splittings MHz B V n abs. freq. MHz 1 1 38 .031786 .038477 Parameters and Errors BJ 1.189257695 { .000001809} BK 3.807933759 { .000156313} B- .134954646 { .000003875} DJ 1.979704E-6 { .021434E-6} DJK -14.138200E-6 { .316215E-6} DK .000000E-6 { fixed } dj .721210E-6 { .021479E-6} dk .000000E-6 { fixed } Vss .000000E-6 { fixed } Vcc .000000E-6 { fixed } mu_y 1.000000000 { fixed } mu_z 5.500000000 { fixed } P_x .000000E-6 { fixed } P_y .000000E-6 { fixed } P_z .000000E-6 { fixed } F 161.298759968 { derived} V1n 5467.202747 { 2.354726} V2n .000000E-6 { fixed } rho .023893605 { derived} beta 2.900679117 { derived} gamma .000000E-6 { derived} F0 157.929000000 { fixed } epsil .000000E-6 { fixed } delta 2.393981550 { .001373846} Standard Deviation .036385 MHz ------------------------------------ B = 1 Rotational Constants and Errors (in GHz) B_z 4.997191454 .000156674 B_x 1.324212342 .000004695 B_y 1.054303049 .000003812 Ray's kappa -.86309 F0(calc) 157.929000000 .000000000 I_alpha 3.200039701 .000000000 <(i,x) <(i,y) <(i,z) 47.1650 90.0000 137.1650 <(i,x) d<(i,y) d<(i,z) .0787 .0000 .0787 V1n_1 2.181585 kj +/- .000940 kj .521050 kcal +/- .000224 kcal 182.366228 cm +/- .0785 cm s= 15.064393 Errors of fitted linear combinations .000001809 .000156313 .000003875 .000000021 .000000316 .000000021 2.354725763 .001373846 Correlation Matrix of fitted linear combinations BJ 1.000 BK -.194 1.000 B- .268 .314 1.000 DJ .811 .162 .295 1.000 DJK .363 -.454 .051 -.113 1.000 dj .390 .146 .909 .477 .015 1.000 V1n_1 .102 -.129 .146 .012 -.030 .124 1.000 delta_ .128 -.189 .196 -.015 .014 .154 .975 1.000 strongest correlation between 8 and 7 ( .9747) Freedom Cofreedom Matrix of linear comb. BJ .279 BK .945 .531 B- .953 .792 .250 DJ .452 .929 .922 .266 DJK .815 .942 .999 .878 .566 dj .923 .851 .364 .861 1.000 .256 V1n_1 .985 .974 .971 .990 .985 .986 .186 delta_ .979 .964 .962 .987 .977 .982 .211 .176 minimum cofreedom between 8 and 7 ( .2110) Eigenvalues and Eigenvector Matrix of SVD-FIT .159687D-01 -.108 .030 -.174 -.061 -.004 -.160 -.659 -.703 .275340D-01 .392 .072 .503 .471 .021 .549 -.186 -.173 .593893D-01 .572 -.146 -.514 .514 .067 -.339 .053 .015 .156664D+00 .334 -.526 .096 -.446 .611 .070 -.147 .059 .415073D+00 .258 .667 .342 -.123 .348 -.485 .012 .012 .104359D+01 .239 -.181 .271 -.130 -.550 -.294 -.494 .433 .277302D+01 -.331 .196 -.224 .285 .403 .152 -.506 .528 .350876D+01 .402 .424 -.450 -.446 -.189 .457 -.081 .080 Stop - Program terminated.