片断：
Theaboveargumentsare,ofcourse,generalones,andapplytoanyrapidly
varyingquantities(phases)whichtakeva luesinfiniteranges.
Returningtotherotationaldegreesoffreedomofmolecules,letusnotethatin
polyatomicgasesthedistributionfunctionmayalsodependontheangleswhich
specifythefixedorientationoftheaxesofthemoleculesrelativetothevectorM.
Forexample,inmoleculesofthesymmetrical-toptypethisistheprecessionangle
betweenMandtheaxisofthetop,whereasthedistributionfunctionmayagainbe
regardedasindependentoftherapidlyvaryinganglesofrotationofthetopabout
itsownaxisandprecessionofthisaxisaboutM.t
Thevibrationalmotionoftheatomswithinthemoleculeispracticallyalways
quantized,sothatthevibrationalstateofthemoleculeisspecifiedbytheap-
propriatequantumnumbers.Underordinaryconditions(atnottoohightem-
peratures),however,thevibrationsarenotexcitedatall,andthemoleculeisatits
groundvibrationallevel.
InthischapterweshalldenotebyFthesetofallvariablesonwhichthe
distributionfunctiondepends,otherthanthecoordinatesofthemoleculeasa
whole(andthetimet).Weseparatefromthephasevolumeelementdrthefactor
dV=dxdydz,anddenotebydFtheremainingfactorintermsofthevariables
used(andintegratedovertheanglesonwhichfdoesnotdepend).ThequantitiesF
haveanimportantcommonproperty:theyareintegralsofthemotion,andremain
constantforeachmoleculeduringitsfreemotion(intheabsenceofanexternal
field)betweensuccessivecollisions;buttheyareingeneralalteredbyeach
collision.Thecoordinatesx,y,zofthemoleculeasawholevary,ofcourse,during
itsfreemotion.
|
