• Non ci sono risultati.

BROGGINI, GIANLUIGIGARANTI LMOLTENI GZECCHI, GAETANO ALDOmostra contributor esterni nascondi contributor esterni 

N/A
N/A
Protected

Academic year: 2021

Condividi "BROGGINI, GIANLUIGIGARANTI LMOLTENI GZECCHI, GAETANO ALDOmostra contributor esterni nascondi contributor esterni "

Copied!
9
0
0

Testo completo

(1). HETEROCYCLES, Vol. 53, No. 4, 2000, pp. 831-839, Received, 3rd December, 1999. ',32/$523+,/,& %(+$9,25 2) 7+( ,62;$=2/( 5,1* ,1 ,175$02/(&8/$51,75,/,0,1(&<&/2$'',7,216  *LDQOXLJL%URJJLQLE/XLVD*DUDQWLD*LRUJLR0ROWHQLD DQG*DHWDQR=HFFKLE  D. 'LSDUWLPHQWRGL&KLPLFD2UJDQLFDH,QGXVWULDOHGHOO¶8QLYHUVLWjDQG&HQWUR&15. 9LD*ROJL0LODQR,WDO\ E. 'LSDUWLPHQWR GL 6FLHQ]H &KLPLFKH )LVLFKH H 0DWHPDWLFKH 8QLYHUVLWj. GHOO ,QVXEULDYLD/XFLQL&RPR,WDO\  $EVWUDFW  8SRQ EDVH WUHDWPHQW ZLWK VLOYHU FDUERQDWH LVR[D]RO\OVXEVWLWXWHG K\GUD]RQR\O FKORULGHV 

(2)  DQG 

(3)  XQGHUJR D VHTXHQWLDO LQWUD LQWHUPROHFXODU QLWULOLPLQHF\FORDGGLWLRQJLYLQJWHWUDF\FOLFS\UD]RO\GLQHGHULYDWLYHV 

(4) DQG 

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

(6)  

(7) DQG 

(8) ZKLFKDUH QRWHDVLO\DFFHVVLEOHE\RWKHUURXWHV  5(68/76$1'',6&866,21 1LWULOLPLQHV 

(9)  ZHUH GHYLVHG DV WKH VXLWDEOH VXEVWUDWHV IRU WKH LQWUDPROHFXODU F\FORDGGLWLRQ RQWR WKH LVR[D]ROHULQJ7KHEXLOGLQJEORFNIRUWKHLUV\QWKHVLVZDVLVR[D]RO\OPHWK\OR[REXWDQRDWH 

(10) ZKLFK ZDV UHDGLO\ SUHSDUHG E\ UHDFWLQJ SURS\Q\O R[REXWDQRDWH 

(11)  ZLWK DQ HTXLPROHFXODU DPRXQW RI WULPHWK\OGLFKORUREHQ]RQLWULOH R[LGH LQ UHIOX[LQJ FDUERQ WHWUDFKORULGH &KORULQDWLRQ RI  DQG VXEVHTXHQW WUHDWPHQW ZLWK WKH GLD]RQLXP VDOW RI WKH DSSURSULDWH DQLOLQH JDYH WKH FRUUHVSRQGLQJ K\GUD]RQR\OFKORULGHV 

(12) 7KHLQVLWXJHQHUDWLRQRIQLWULOLPLQHV 

(13) ZDVSHUIRUPHGE\WUHDWLQJD0  .

(14) . . Scheme 1.  Ar. . O. O. . N. Ar. SO2Cl 2 0-5°C. O. O. 2. 1. . O. N. CCl 4, ∆. O. . O. O.   N 2 Cl.  . Cl Ar. X O.  . NH. N. O. O. Ag2CO 3. X. N. O. 0-5°C. O. O. . Cl. . O. Ar. 3. dioxane, 75°C. N. . 4.    . O. O X. N. N. N. X. N. O. . O. Ar. O. . N. . O. N. Ar. 5. 6.  . 5. . Ar. . X. . Ar. N O. . 9.  Me. N Me. Cl. a: X = H; b: X = Me; c: X = Cl. N O. N. Cl. Ar = Me. . COO Ar.  . OH. N. N. N O O. O 7. X.

(15)  VROXWLRQ RI  LQ GU\ GLR[DQH DW ƒ& 5HDFWLRQ WLPHV HOXDQWV DQG SURGXFW \LHOGV DUH JLYHQ LQ 7DEOH  ZKLOHDQDO\WLFDODQGVSHFWURVFRSLFGDWDDUHFROOHFWHGLQ7DEOHVDQG  7DEOH5HDFWLRQRIK\GUD]RQR\OFKORULGHV 

(16) LQWKHSUHVHQFHRIVLOYHUFDUERQDWH BBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBB BBBB. . . &RPSG. 7LPHD K

(17) . 3URGXFWVDQG\LHOGV 

(18) E. BBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBB BB. . (OXHQWF.      BBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBB       (W2/3G 

(19)  D        (W2/3G 

(20)  E        $F2(W/3G 

(21)  F BBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBB    D,Q GU\ GLR[DQH DW ƒ& E,VRODWLRQ \LHOGV RI SXUH SURGXFWV F6LOLFD JHO FROXPQ FKURPDWRJUDSK\ G/3 OLJKWSHWUROHXPESƒ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

(22)  IROORZHG E\ DQ LQWHUPROHFXODU F\FORDGGLWLRQ RI  RQWR WKH ILUVWIRUPHG F\FORDGGXFWV 

(23) 6XUSULVLQJO\WKHDERYHFRQGLWLRQVSUHFOXGHGWKHLVRODWLRQRIWKHODWWHUVSHFLHV+RZHYHU FRPSRXQGV 

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

(25) ZKLFKZDVWKHQVXEPLWWHGWRWKH VLOYHU FDUERQDWH WUHDWPHQW 6FKHPH 

(26)  %HVLGHV WKH IRUPDWLRQ RI VRPH TXDQWLW\ RI PHWK\O K\GUR[\PHWK\OLVR[D]ROH 

(27) WKHRQO\GHWHFWDEOHF\FORDGGLWLRQSURGXFWZDVDJDLQD7$'3QDPHO\ .

(28)  7DEOH&KDUDFWHULVDWLRQIRUFRPSRXQGV 

(29) DQG 

(30) D. BBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBB. PSE ƒ&

(31) . &RPSG )RUPXOD

(32) . 0LFURDQDO\VHV. BBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBB. 06 P]. & + 1 0

(33)  IRXQG IRXQG IRXQG FDOFG FDOFG FDOFG BBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBB              D &+12&O

(34)                     E &+12&O

(35)                     F &+12&O

(36)                            &+12&O

(37)  BBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBB        D105GDWDDUHJLYHQLQ7DEOHE)URPGLLVRSURS\OHWKHU . . ,5 QXMRO

(38)  ν FP

(39) . . .   7DEOH+105GDWDIRUFRPSRXQGV 

(40) DQG 

(41) . BBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBB. &RPSG.  . . +105 &'&O

(42)  δ-D BBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBB    +V

(43)  +V

(44)  +V

(45)  +G- 

(46)  +G- 

(47)  D +V

(48)  +G- 

(49)  +G- 

(50)  +V

(51)  +P

(52)     +V

(53)  +V

(54)  +V

(55)  +V

(56)  +V

(57)  +G- 

(58)  E  +G- 

(59)  +V

(60)  +G- 

(61)  +G- 

(62)  + V

(63)  +P

(64)     +V

(65)  +V

(66)  +V

(67)  +G- 

(68)  +G- 

(69)  F +V

(70)  +G- 

(71)  +G- 

(72)  +V

(73)  +P

(74)     +V

(75)  +V

(76)  +EUV

(77)  +V

(78)  +V

(79)   BBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBB   D&RXSOLQJFRQVWDQWVDUHJLYHQLQ+].

(80)   Scheme 2. Me. . O.  1. +. PhNCO/Et 3N. NO2. SO2Cl 2. N. toluene, 0°C. 10. . Cl.  Me O. . Ar. O Ar. N. NH. dioxane, 75°C. O. Cl O. Me. N 12.  . . Ag2CO 3. O. 11. . . N. N2 Cl 0-5°C. O. O. . . 0-5°C. O. O. . . O. Me. Ar O Ar. N. Me. Ar Me. N. N. N O. N. Me. N. (13) N. O. . N. O. 13. . O. N O. N. N N. O. Ar O. O. O. O. O. 15 (48%). 14.     . Me. N O. OH. Ar =. Cl. 16 (28%). 7KHUHIRUHLWFDQEHDUJXHGWKDWWKHVLWHVHOHFWLYLW\RIWKHLQWHUPROHFXODUF\FORDGGLWLRQLVGLFWDWHGE\WKH HOHFWURQLF GHPDQGV RI WKH GLSRODURSKLOLF VLWHV RI  DQG  UDWKHU WKDQ E\ VWHULF HQFXPEUDQFH DW WKH LVR[D]ROLQLF& 1ERQG $VIDUWKHVLGHIRUPDWLRQRIFRPSRXQGV 

(81) DQG 

(82) RQHFDQQRWHWKDWWKH\UHIOHFWDNQRZQGHJUDGDWLYH SURFHVV RI QLWULOLPLQHV ZKLFK LV LOOXVWUDWHG LQ 6FKHPH  3UHFHGHQWV RI VXFK EHKDYLRXU SDWWHUQ DUH DYDLODEOHLQWKHOLWHUDWXUH  . Scheme 3 R.   . O 5 or 13. Ar. NH2. +. 9 or 16 N O. O 8. . CN.

(83)  $VDIXUWKHUVWDJHRIRXUZRUNZHXQGHUWRRNDFRPSXWDWLRQDOVWXG\DWWKH$0OHYHORIQLWULOLPLQH 

(84)  DQGF\FORDGGXFW 

(85) 7KHUHVXOWVJLYHQLQ)LJXUHLQGLFDWHWKDWQLWULOLPLQH 

(86) VKRXOGDWWDFNSUHIHUDEO\ WKH& 1S\UD]ROLQLFERQGUDWKHUWKDQWKHLVR[D]ROLQLFRQHE\ZD\RID+202GLSROHFRQWUROOHGSURFHVV 7KLVMXVWDFFRXQWVIRUH[SHULPHQWDOHYLGHQFH  . 13. 14.   . N E (eV). N. O. N. N. N.  . -0.091. 0. . -0.925. -0.976.      . -8.667.  . -10.56.  . -10.08. Figure 1. FMO energies calculated with the AM1 method..   (;3(5,0(17$/ 0HOWLQJSRLQWVZHUHGHWHUPLQHGZLWKD%FKLDSSDUDWXVDQGDUHXQFRUUHFWHG,5VSHFWUDZHUHUHFRUGHGRQ D )7 ,5 3HUNLQ (OPHU  ; VSHFWURSKRWRPHWHU 06 VSHFWUD ZHUH GHWHUPLQHG ZLWK D 9*(4 DSSDUDWXV +105 VSHFWUD ZHUH WDNHQ ZLWK D %UXNHU $&  RU $0;  LQVWUXPHQW LQ &'&O VROXWLRQVFKHPLFDOVKLIWVDUHJLYHQDVSSPIURP0H6LDQG-YDOXHVDUHJLYHQLQ+]  > 7ULPHWK\OGLFKORURSKHQ\O

(87) LVR[D]RO\O@PHWK\O R[REXWDQRDWH 

(88)  $ VROXWLRQ RI   J  PPRO

(89)  DQG WULPHWK\OGLFKORUREHQ]RQLWULOR[LGH  J  PPRO

(90)  LQ WHWUDFKORURPHWKDQH  P/

(91)  ZDV UHIOX[HG IRU  K (YDSRUDWLRQ RI WKH VROYHQW DQG VXEVHTXHQW FU\VWDOOLVDWLRQ IURP GLLVRSURS\O HWKHU JDYH  \LHOG  J 

(92)  PS ƒ& ,5 1XMRO

(93)    .

(94)  FP

(95)  +105δ +V

(96)  +V

(97)  +V

(98)  +V

(99)  +V

(100)  +V

(101) 06 P] 0

(102) $QDO&DOFGIRU&+12&O&+1)RXQG&+1   0HWK\OLVR[D]RO\O

(103) PHWK\O R[REXWDQRDWH 

(104)  $ VROXWLRQ RI   J  PPRO

(105)  QLWURHWKDQH  J  PPRO

(106)  DQG WULHWK\ODPLQH  J  PPRO

(107)  LQ GU\ WROXHQH  P/

(108)  ZDV FRROHG WR ƒ& 3KHQ\OLVRF\DQDWH JPPRO

(109) ZDVDGGHGGURSZLVHXQGHU YLJRURXV VWLUULQJ DQG FRROLQJ DW ƒ& $IWHUKWKHUHDFWLRQPL[WXUHZDVDOORZHGWRZDUPWRUWRYHUQLJKW7KHVROLGPDWHULDOZDVILOWHUHGRII ZDVKHGZLWKWROXHQH P/

(110) DQGWKHFRPELQHGILOWUDWHVZDVHYDSRUDWHGJLYLQJDVXQGLVWLOODEOHRLOQRW DQDO\WLFDOO\SXUH\LHOGJ 

(111) ,5 1HDW

(112)  FP

(113) +105δ +V

(114)  +V

(115)   +V

(116)  +V

(117)  +V

(118) 06P] 0

(119)   > 7ULPHWK\OGLFKORURSKHQ\O

(120) LVR[D]RO\O@PHWK\O FKORURR[REXWDQRDWH 

(121)  DQG  0HWK\OLVR[D]RO\O

(122) PHWK\OFKORURR[REXWDQRDWH 

(123) *HQHUDO3URFHGXUH$VROXWLRQRIVXOIXU\O FKORULGH JPPRO

(124) LQGU\FKORURIRUP P/

(125) ZDVVORZO\DGGHG K

(126) WRDPL[WXUHRIRU PPRO

(127) DQGVRGLXPK\GURJHQFDUERQDWH JPPRO

(128) LQGU\FKORURIRUP P/

(129) NHHSLQJWKH WHPSHUDWXUH LQ WKH UDQJH ƒ& $IWHU  K DW UW FKORURIRUP  P/

(130)  ZDV DGGHG DQG WKH PL[WXUH ZDV ZDVKHG ZLWK ZDWHU × P/

(131)  7KH RUJDQLF OD\HU ZDV GULHG RYHU VRGLXP VXOIDWH DQG WKH VROYHQW ZDV UHPRYHGXQGHUUHGXFHGSUHVVXUHJLYLQJRUDVXQGLVWLOODEOHRLOVQRWDQDO\WLFDOO\SXUH 

(132) \LHOGJ 

(133) ,5 1HDW

(134)  FP

(135) +105δ +V

(136)  +V

(137)  +V

(138)   +V

(139)  +V

(140)  +V

(141) 06P] 0

(142)  

(143) \LHOGJ 

(144) ,5 1HDW

(145)  FP

(146) +105δ +V

(147)  +V

(148)  +V

(149)   +V

(150)  +V

(151) 06P] 0

(152)   +\GUD]RQR\O FKORULGHV 

(153)  DQG 

(154)  *HQHUDO 3URFHGXUH $ VROXWLRQ RI  RU   PPRO

(155)  LQ FROG PHWKDQRO P/

(156) ZDVDGGHGZLWKVRGLXPDFHWDWH  J  PPRO

(157)  $ FROG DTXHRXV VROXWLRQ RI WKH DSSURSULDWH DUHQHGLD]RQLXP FKORULGH  PPRO

(158)  ZDV DGGHG GURSZLVH XQGHU YLJRURXV VWLUULQJ DQG LFH FRROLQJ7KHPL[WXUHZDVDOORZHGWRVWDQGRYHUQLJKWDWUW7KHVROYHQZDVSDUWO\UHPRYHGXQGHUUHGXFHG SUHVVXUH DQG WKH UHVXOWLQJ PL[WXUH ZDV H[WUDFWHG ZLWK HWKHU × P/

(159)  7KH RUJDQLF OD\HU ZDV ZDVKHG ILUVWO\ZLWKDTXHRXVVRGLXP K\GURJHQFDUERQDWH  P/

(160)  WKHQ ZLWK ZDWHU  P/

(161)  DQG GULHG RYHU VRGLXPVXOIDWH(YDSRUDWLRQRIWKHVROYHQWDQGVXEVHTXHQWFU\VWDOOLVDWLRQIURPGLLVRSURS\OHWKHUJDYHWKH K\GUD]RQR\OFKORULGHV 

(162) RU 

(163) LQWKHSXUHVWDWH. .

(164)  D

(165) \LHOGJ 

(166) PSƒ&,5 1XMRO

(167)  FP

(168) +105δ +V

(169)  +V

(170)   + V

(171)   + V

(172)   + P

(173)   + EU V

(174)  06 P]  0

(175)  $QDO &DOFG IRU &+12&O&+1)RXQG&+1 E

(176) \LHOGJ 

(177) PSƒ&,5 1XMRO

(178)  FP

(179) +105δ +V

(180)  +V

(181)   +V

(182)  +V

(183)  +V

(184)  +P

(185)  +EUV

(186) 06P] 0

(187) $QDO&DOFG IRU&+12&O&+1)RXQG&+1 F

(188) \LHOGJ 

(189) PSƒ&,5 1XMRO

(190)  FP

(191)  +105δ +V

(192)  +V

(193)   + V

(194)   + V

(195)   + P

(196)   + EU V

(197)  06 P]  0

(198)  $QDO &DOFG IRU &+12&O&+1)RXQG&+1 

(199) \LHOGJ 

(200) PSƒ&,5 1XMRO

(201)  FP

(202)  +105δ +V

(203)  +V

(204)   +V

(205)  +P

(206)  +EUV

(207) 06P] 0

(208) $QDO&DOFGIRU&+12&O& +1)RXQG&+1  6LOYHUFDUERQDWHWUHDWPHQWRIK\GUD]RQR\OFKORULGHV 

(209) DQG 

(210) *HQHUDO3URFHGXUH$VROXWLRQRI RU PPRO

(211) LQGU\GLR[DQH P/

(212) ZDVWUHDWHGZLWKVLOYHUFDUERQDWH JPPRO

(213) DQG WKHPL[WXUHZDVVWLUUHGLQWKHGDUNDWƒ&IRUWKHWLPHLQGLFDWHGLQ7DEOH IRUFRPSRXQGV 

(214)

(215) RUK IRUFRPSRXQG 

(216)

(217) 7KHXQGLVVROYHGPDWHULDOZDVILOWHUHGRIIWKHVROYHQWZDVHYDSRUDWHGDQGWKHQWKH UHVLGXH ZDV FKURPDWRJUDSKHG RQ D VLOLFD JHO FROXPQ ZLWK WKH HOXHQWV JLYHQ LQ 7DEOH  IRU FRPSRXQGV 

(218)

(219)  RU ZLWK HWK\O DFHWDWHKH[DQH  IRU FRPSRXQG 

(220)

(221)  &\FORDGGXFWV 

(222)  RU 

(223)  ZDV HOXWHG ILUVWO\ IROORZHGE\RU$QDO\WLFDODQGVSHFWUDOGDWDRIFRPSRXQGV 

(224) DQG 

(225) DUHFROOHFWHGLQ7DEOHVDQG  

(226) \LHOGJ 

(227) PSƒ&,5 1XMRO

(228)  FP

(229)  +105δ +V

(230)  +V

(231)   +G- 

(232)  +G- 

(233)  +V

(234)  +G- 

(235)  +G- 

(236)  + V

(237)   + P

(238)  06 P]  0

(239)  $QDO &DOFG IRU &+12&O &  +  1 )RXQG&+1  > 7ULPHWK\OGLFKORUR

(240) SKHQ\O@K\GUR[\PHWK\OLVR[D]ROH 

(241) $VROXWLRQRIWULPHWK\O GLFKORUREHQ]RQLWULOR[LGH  J  PPRO

(242)  DQG SURS\QRO  J  PPRO

(243)  LQ WHWUDFKORURPHWKDQH  P/

(244)  ZDV UHIOX[HG IRU  K (YDSRUDWLRQ RI WKH VROYHQW DQG VXEVHTXHQW FU\VWDOOLVDWLRQIURPGLLVRSURS\OHWKHUJDYH\LHOGJ 

(245)   $&.12:/('*(0(176 :HWKDQN08567DQG&15IRUILQDQFLDOVXSSRUW  .

(246)  5()(5(1&(6 . 3 &DUDPHOOD DQG 3 *UQDQJHU 'LSRODU &\FORDGGLWLRQ &KHPLVWU\  HG E\ $ 3DGZD :LOH\ ,QWHUVFLHQFH1HZ<RUN9RO&KDSWHU. . 3$:DGH &RPSUHKHQVLYH2UJDQLF6\QWKHVLV 9ROHGE\%7URVWDQG,)OHPLQJ3HUJDPRQ 3UHVV1HZ<RUN&KDSWHUSS. . 3 . &ODXV 0HWKRGHQ GHU 2UJDQLVFKH &KHPLH +RXEHQ:HLO

(247)  HG E\ ' .ODPDQQ DQG + +DJHPDQQ*HRUJ7KLHPH9HUODJ6WXWWJDUW%DQG(E7HLOSS. . *=HFFKL7UHQGV+HWHURF\FO&KHP. . $66KDZDOL&KHP5HY. . *%URJJLQL*0ROWHQLDQG*=HFFKL+HWHURF\FOHV. . *%URJJLQL*0ROWHQLDQG*=HFFKL-&KHP5HV 6

(248) . . *%URJJLQL/*DUDQWL*0ROWHQLDQG*=HFFKL-&KHP6RF3HUNLQ7UDQV. . $FFRUGLQJ WR WKH UHSODFHPHQW UXOH QRPHQFODWXUH WKH IXOO QDPH RI FRPSRXQG D

(249)  VKRXOG EH ELV SKHQ\O

(250) > WULPHWK\OGLFKORUR

(251) SKHQ\O@R[RDGLK\GUR+R[DD]D 5,6a,7-tetraazadicyclopenta[a,h]pentalene-6-carboxilic acid 3-[(2,4,6-trimethyl-3,5GLFKORUR

(252) SKHQ\O@LVR[D]RO\OPHWK\OHVWHU,QRUGHUWRDYRLGVXFKDZNZDUGQDPHZHSURSRVHWKH achronym TADP, standing for TetraAzaDicyclopentaPentalene for both compounds (7 )and (15)..  51/DFH\-&KHP6RF  3%HOWUDPH&9HJOLRDQG06LPRQHWWD-&KHP6RF %

(253)   -3*LEHUW&3pWUXVDQG)3pWUXV-+HWHURF\FO&KHP  /-%HOODP\ 7KH,QIUDUHG6SHFWUDRI&RPSOH[0ROHFXOHV 0HWKXHQ/RQGRQ&KDSWHU  $4XLOLFRDQG/3DQL]]L*D]]&KLP,WDO  D

(254) 1+7RXEURDQG$+ROP-$PHU&KHP6RF E

(255) /*DUDQWL*0ROWHQL DQG*=HFFKL+HWHURF\FOHV F

(256) /*DUDQWL*0ROWHQLDQG*=HFFKL+HWHURF\FOHV   $VLPSOHPHQWHGLQWKH+\SHUFKHPSDFNDJHRISURJUDPV  0-6'HZDU(*=RHELVFK()+HDO\DQG--36WHZDUW-$PHU&KHP6RF . .

(257)

Riferimenti

Documenti correlati

Turning to the issue of selecting an appropriate sampling algorithm, it is common lore that using a single electron move implementation of the Langevin algorithm 11 provides a

We focus on the characterization of the orbitals in the excited state wave functions, on the electronic density evolution from the united atom to dissociation, on

Motivation for this work comes not only from obtaining potential energy curves for the high excited states of H 2 but also from characterizing the electronic density evolution from

We aim (a) at the evaluation of the PECs starting at very short and unexplored internuclear distances (0.01 bohrs) and ending at full dissociation, (b) at the systematic prediction

The Galois closure of γ¯ is non-fibred We are going to prove that for a general choice of the abelian surface S with the 1, 2polarization, the associated LG surface X does not

1 corresponding to a horizontal rigid displacement ⌬r=100 ␮ m of all the tracking particles: 共a兲 differential heterodyne signal ␦ f 12 共r兲, appearing as uniform speckle

Given the ease with which the appropriate deterministic benchmarks can be generated, and the fact that the convergence of parallel tempering on these systems has been measured

One AD patient (CE) showed a significant category effect on all three tasks with disproportionately worse performances on living items than on non-living ones; another patient