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 1 rofit .0000000D+00 eps .1000000D-11 defer .1000000D-04 weigf .0000000D+00 convg .9990000D+00 lambda .1000000D-04 freq_l .6000000D+01 freq_h .1900000D+02 limit .1000000D+00 temp .2000000D+01 Using Watson S 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 1.467250650 BK 2.749404350 B- .241540250 DJ .225000E-6 DJK 6.310000E-6 mu_x .300000000 mu_y 1.500000000 mu_z 4.900000000 F 160.301452429 V1n 4619.154361 rho .017955177 beta 2.630418189 Dpi2J -.000119231 F0 157.690000000 delta 2.196459826 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 Dpi2J_1 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 28 Data Points 28 Splittings 0 Effective Data Points 1.1 \\ Maximal K = J = 7 \\ B= 1 adj= 25 \\ (1) calculate torsional integrals \\ (32)use torsional integrals in rigid rotor H_rr Sigma: .550566D-02 Sigma/OldSigma: .000000 conv: 1 J K- K+ J K- K+ Sym calc/GHz diff/MHz obs/GHz 1: 3 1 3 2 1 2 /A 8.0432798 -1.7228 8.0415570 Err .5D-04 /A -/A 2: 3 0 3 2 0 2 /A 8.5599477 -2.7577 8.5571900 Err .5D-04 /A -/A 3: 3 2 2 2 2 1 /A 8.8069976 -3.6616 8.8033360 Err .5D-04 /A -/A 4: 3 2 1 2 2 0 /A 9.0542051 -4.5771 9.0496280 Err .5D-04 /A -/A 5: 3 1 2 2 1 1 /A 9.4908735 -5.3155 9.4855580 Err .5D-04 /A -/A 6: 4 1 4 3 1 3 /A 10.6614264 -2.0754 10.6593510 Err .5D-04 /A -/A 7: 4 0 4 3 0 3 /A 11.1639637 -2.8397 11.1611240 Err .5D-04 /A -/A 8: 4 2 3 3 2 2 /A 11.6930097 -4.6967 11.6883130 Err .5D-04 /A -/A 9: 4 1 3 3 1 2 /A 12.5673449 -6.7419 12.5606030 Err .5D-04 /A -/A 10: 5 1 5 4 1 4 /A 13.2389907 -2.3017 13.2366890 Err .5D-04 /A -/A 11: 5 0 5 4 0 4 /A 13.6437421 -2.6591 13.6410830 Err .5D-04 /A -/A 12: 5 2 4 4 2 3 /A 14.5372696 -5.5776 14.5316920 Err .5D-04 /A -/A 13: 5 1 4 4 1 3 /A 15.5537937 -7.7987 15.5459950 Err .5D-04 /A -/A 14: 5 2 3 4 2 2 /A 15.5691740 -9.0250 15.5601490 Err .5D-04 /A -/A 15: 6 1 6 5 1 5 /A 15.7790180 -2.4280 15.7765900 Err .5D-04 /A -/A 16: 6 0 6 5 0 5 /A 16.0592483 -2.4773 16.0567710 Err .5D-04 /A -/A 17: 6 2 5 5 2 4 /A 17.3313137 -6.2787 17.3250350 Err .5D-04 /A -/A 18: 7 1 7 6 1 6 /A 18.2883303 -2.4903 18.2858400 Err .5D-04 /A -/A 19: 6 1 5 5 1 4 /A 18.4133623 -8.3413 18.4050210 Err .5D-04 /A -/A 20: 7 0 7 6 0 6 /A 18.4620208 -2.3988 18.4596220 Err .5D-04 /A -/A 21: 4 K -1 3 K -1 /E 10.6620799 -2.1499 10.6599300 Err .5D-04 /E -/E 22: 4 K 0 3 K 0 /E 11.1580773 -2.5573 11.1555200 Err .5D-04 /E -/E 23: 4 K 1 3 K 1 /E 12.5432747 -5.4247 12.5378500 Err .5D-04 /E -/E 24: 5 K -1 4 K -1 /E 13.2364696 -2.1996 13.2342700 Err .5D-04 /E -/E 25: 5 K 0 4 K 0 /E 13.6399715 -2.6515 13.6373200 Err .5D-04 /E -/E 26: 5 K 1 4 K 1 /E 15.5270917 -6.3317 15.5207600 Err .5D-04 /E -/E 27: 6 K -1 5 K -1 /E 15.7753034 -2.2634 15.7730400 Err .5D-04 /E -/E 28: 6 K 0 5 K 0 /E 16.0561311 -2.5411 16.0535900 Err .5D-04 /E -/E Maximum (obs-calc)/err in line 14 .0090250 indep.par: 8 stepw:1.0000 lambda: .400D-05 cond.no: .885D+02 ------------------------------------------------------- Iteration : 1 Sigma: .254999D-04 Sigma/OldSigma: .004632 conv: 1 Parameters Change BJ 1.466665920 { -.000584730} BK 2.746105579 { -.003298771} B- .240962725 { -.000577525} DJ .251142E-6 { .026142E-6} DJK 6.115094E-6 { -.194906E-6} mu_x .300000000 { fixed } mu_y 1.500000000 { fixed } mu_z 4.900000000 { fixed } F 160.313278984 { derived} V1n 4678.504586 { 59.350225} rho .018029295 { derived} beta 2.635397636 { derived} Dpi2J -.000124844 { -.000005613} F0 157.690000000 { fixed } delta 2.202141812 { .005681986} DJ (1) .251142E-6 .026142E-6 10.409% Max. Change indep.par: 8 stepw:1.0000 lambda: .160D-05 cond.no: .888D+02 ------------------------------------------------------- Iteration : 2 Sigma: .249273D-04 Sigma/OldSigma: .977545 conv: 1 Parameters Change BJ 1.466666636 { .000000716} BK 2.746109548 { .000003968} B- .240963505 { .000000780} DJ .250250E-6 { -.000892E-6} DJK 6.113354E-6 { -.001740E-6} mu_x .300000000 { fixed } mu_y 1.500000000 { fixed } mu_z 4.900000000 { fixed } F 160.314372616 { derived} V1n 4678.814279 { .309693} rho .018036282 { derived} beta 2.635791057 { derived} Dpi2J -.000125798 { -.000000955} F0 157.690000000 { fixed } delta 2.202583911 { .000442100} Dpi2J_1(1) -.000125798 -.000000955 .759% Max. Change indep.par: 8 stepw:1.0000 lambda: .640D-06 cond.no: .888D+02 ------------------------------------------------------- Iteration : 3 Sigma: .249273D-04 Sigma/OldSigma:1.000000 conv: 2 Parameters Change BJ 1.466666636 { .000000000} BK 2.746109545 { -.000000002} B- .240963505 { .000000000} DJ .250251E-6 { .000001E-6} DJK 6.113348E-6 { -.000006E-6} mu_x .300000000 { fixed } mu_y 1.500000000 { fixed } mu_z 4.900000000 { fixed } F 160.314372648 { derived} V1n 4678.816364 { .002086} rho .018036282 { derived} beta 2.635791069 { derived} Dpi2J -.000125798 { .000000000} F0 157.690000000 { fixed } delta 2.202583925 { .000000014} DJ (1) .250251E-6 .000001E-6 .000% Max. Change indep.par: 8 stepw:1.0000 lambda: .256D-06 cond.no: .888D+02 ------------------------------------------------------- Iteration : 4 Sigma: .249273D-04 Sigma/OldSigma:1.000000 conv: 3 DJ (1) .250251E-6 .000000E-6 .000% Max. Change indep.par: 8 stepw:1.0000 lambda: .256D-06 cond.no: .888D+02 Recalculation of the spectrum ######################################################### End at Cycle 4 J K- K+ J K- K+ Sym calc/GHz diff/MHz obs/GHz 1: 3 1 3 2 1 2 /A 8.0415627 -.0057 8.0415570 Err .5D-04 /A -/A 2: 3 0 3 2 0 2 /A 8.5571928 -.0028 8.5571900 Err .5D-04 /A -/A 3: 3 2 2 2 2 1 /A 8.8033362 -.0002 8.8033360 Err .5D-04 /A -/A 4: 3 2 1 2 2 0 /A 9.0496324 -.0044 9.0496280 Err .5D-04 /A -/A 5: 3 1 2 2 1 1 /A 9.4855628 -.0048 9.4855580 Err .5D-04 /A -/A 6: 4 1 4 3 1 3 /A 10.6593575 -.0065 10.6593510 Err .5D-04 /A -/A 7: 4 0 4 3 0 3 /A 11.1611238 .0002 11.1611240 Err .5D-04 /A -/A 8: 4 2 3 3 2 2 /A 11.6883119 .0011 11.6883130 Err .5D-04 /A -/A 9: 4 1 3 3 1 2 /A 12.5606057 -.0027 12.5606030 Err .5D-04 /A -/A 10: 5 1 5 4 1 4 /A 13.2366954 -.0064 13.2366890 Err .5D-04 /A -/A 11: 5 0 5 4 0 4 /A 13.6410792 .0038 13.6410830 Err .5D-04 /A -/A 12: 5 2 4 4 2 3 /A 14.5316882 .0038 14.5316920 Err .5D-04 /A -/A 13: 5 1 4 4 1 3 /A 15.5459925 .0025 15.5459950 Err .5D-04 /A -/A 14: 5 2 3 4 2 2 /A 15.5601554 -.0064 15.5601490 Err .5D-04 /A -/A 15: 6 1 6 5 1 5 /A 15.7765957 -.0057 15.7765900 Err .5D-04 /A -/A 16: 6 0 6 5 0 5 /A 16.0567661 .0049 16.0567710 Err .5D-04 /A -/A 17: 6 2 5 5 2 4 /A 17.3250276 .0074 17.3250350 Err .5D-04 /A -/A 18: 7 1 7 6 1 6 /A 18.2858452 -.0052 18.2858400 Err .5D-04 /A -/A 19: 6 1 5 5 1 4 /A 18.4050086 .0124 18.4050210 Err .5D-04 /A -/A 20: 7 0 7 6 0 6 /A 18.4596188 .0032 18.4596220 Err .5D-04 /A -/A 21: 4 K -1 3 K -1 /E 10.6599573 -.0273 10.6599300 Err .5D-04 /E -/E 22: 4 K 0 3 K 0 /E 11.1554527 .0673 11.1555200 Err .5D-04 /E -/E 23: 4 K 1 3 K 1 /E 12.5378379 .0121 12.5378500 Err .5D-04 /E -/E 24: 5 K -1 4 K -1 /E 13.2342549 .0151 13.2342700 Err .5D-04 /E -/E 25: 5 K 0 4 K 0 /E 13.6373482 -.0282 13.6373200 Err .5D-04 /E -/E 26: 5 K 1 4 K 1 /E 15.5207853 -.0253 15.5207600 Err .5D-04 /E -/E 27: 6 K -1 5 K -1 /E 15.7729958 .0442 15.7730400 Err .5D-04 /E -/E 28: 6 K 0 5 K 0 /E 16.0536370 -.0470 16.0535900 Err .5D-04 /E -/E Maximum (obs-calc)/err in line 22 .0000673 RMS deviations (MHz), B and V sorted B V n splittings MHz B V n abs. freq. MHz 1 1 28 .020534 .026401 Parameters and Errors BJ 1.466666636 { .000001830} BK 2.746109545 { .000059745} B- .240963505 { .000001829} DJ .250251E-6 { .027530E-6} DJK 6.113348E-6 { .594098E-6} DK .000000E-6 { fixed } dj .000000E-6 { fixed } dk .000000E-6 { fixed } Vss .000000E-6 { fixed } Vcc .000000E-6 { fixed } mu_x .300000000 { fixed } mu_y 1.500000000 { fixed } mu_z 4.900000000 { fixed } P_x .000000E-6 { fixed } P_y .000000E-6 { fixed } P_z .000000E-6 { fixed } F 160.314372648 { derived} V1n 4678.816364 { 1.166458} V2n .000000E-6 { fixed } rho .018036282 { derived} beta 2.635791069 { derived} gamma .000000E-6 { derived} Dpi2J -.000125798 { .000002871} F0 157.690000000 { fixed } epsil .000000E-6 { fixed } delta 2.202583925 { .000991756} Standard Deviation .024927 MHz ------------------------------------ B = 1 Rotational Constants and Errors (in GHz) B_z 4.212776181 .000060272 B_x 1.707630140 .000002659 B_y 1.225703131 .000002513 Ray's kappa -.67732 F0(calc) 157.690000000 .000000000 I_alpha 3.204889784 .000000000 <(i,x) <(i,y) <(i,z) 36.1988 90.0000 126.1988 <(i,x) d<(i,y) d<(i,z) .0568 .0000 .0568 V1n_1 1.866994 kj +/- .000465 kj .445913 kcal +/- .000111 kcal 156.068493 cm +/- .0389 cm s= 12.971226 Errors of fitted linear combinations .000001830 .000059745 .000001829 .000000028 .000000594 .000002871 1.166457530 .000991756 Correlation Matrix of fitted linear combinations BJ 1.000 BK -.274 1.000 B- .056 .278 1.000 DJ .429 .201 -.491 1.000 DJK .495 -.316 .306 -.393 1.000 Dpi2J_ -.453 -.022 .070 -.217 -.044 1.000 V1n_1 .068 -.155 -.434 .202 -.169 -.408 1.000 delta_ .207 .135 .452 -.018 -.109 -.328 -.226 1.000 strongest correlation between 5 and 1 ( .4946) Freedom Cofreedom Matrix of linear comb. BJ .263 BK .794 .515 B- .859 .795 .440 DJ .574 .783 .751 .276 DJK .659 .903 .925 .721 .377 Dpi2J_ .867 .931 .944 .932 .973 .626 V1n_1 .996 .994 .943 .986 .982 .918 .760 delta_ .975 .995 .934 .992 .952 .951 .960 .681 minimum cofreedom between 4 and 1 ( .5745) Eigenvalues and Eigenvector Matrix of SVD-FIT .481309D-01 .740 -.054 -.138 .627 .083 -.162 .059 .034 .641634D-01 -.435 .182 -.332 .541 -.602 .039 .078 -.059 .160972D+00 -.069 -.568 -.656 -.117 .203 .078 .204 -.373 .312633D+00 -.076 .309 .029 .275 .417 .596 -.334 -.425 .426394D+00 .108 -.589 .156 .054 -.340 .509 -.395 .289 .927108D+00 .136 -.116 .490 .003 -.260 .254 .620 -.460 .178650D+01 .078 -.122 .150 -.066 -.275 -.453 -.543 -.613 .427410D+01 -.465 -.413 .390 .466 .395 -.286 .044 .063 Stop - Program terminated.