The existence of Xe≡N

(1) XeNOF 、 ArNOF and KrNOF

Table 1.Calculated Bond Lengths (Å) and Bond Angles (º) of XeNOF 、 ArNOF and KrNOF

			XeNOF
Method	Xe-N	Xe-O	Xe-F	N-Xe-O	N-Xe-F	O-Xe-F
MP2/apdz	1.794	1.787	1.990	124.0	103.1	100.7
MP2/aptz	1.769	1.763	1.964	119.5	119.5	101.1
CCSD/aptz	1.784	1.788	1.997	115.2	111.5	93.9
B3LYP/apdz	1.838	1.861	2.100	118.1	113.3	96.6
B3LYP/aptz	1.805	1.817	2.059	115.7	111.8	96.9
MPW1PW91/apdz	1.815	1.836	2.065	117.9	112.7	95.5
MPW1PW91/aptz	1.785	1.794	2.020	115.4	111.4	95.6

			ArNOF
Method	Ar-N	Ar-O	Ar-F	N-Ar-O	N-Ar-F	O-Ar-F
MP2/apdz	1.477	1.501	1.824	123.8	109.3	98.0
MP2/aptz	1.429	1.461	1.802	124.2	107.4	99.0
B3LYP/apdz	1.561	1.647	2.025	122.7	111.7	100.1
B3LYP/aptz	1.503	1.577	1.979	122.5	111.0	99.2

			KrNOF
Method	Kr-N	Kr-O	Kr-F	N-Kr-O	N-Kr-F	O-Kr-F
MP2/apdz	1.607	1.618	1.888	124.4	105.7	99.2

Table 2.Calculated Energies (kcal/mol) Relative to XeNOF、ArNOF and KrNOF

XeNOF	triplet state	Xe + N(Q) + O(T) + F	Xe + N(D) + O(S) + F	XeO + NF	TS	Xe + F(D) + NO(D)	TS	Xe + N(D) + OF(D)	TS
MP2/apdz	62.7	-14.8	131.6	-14.7	45.4	-157.2	48.6	19.7	76.2
MP2/aptz	63.5	24.1	165.5	1.9	48.7	-129.3	57.9	47.9	77.7
MP2/aptz//MP2/apdz	60.6	23.0	164.3	1.6	48.8	-130.4		46.8	77.5
CCSD/apdz//MP2/apdz	38.8	-58.4	67.2	-46.5	17.4	-184.7		-26.2	58.7
CCSD/aptz//MP2/apdz	37.6	-28.8	92.6	-34.3	20.9	-164.9		-5.6	60.0
CCSD/aptz		-26.3	95.1	-31.9		-162.4		-3.1
CCSD(T)/apdz//MP2/apdz	48.2	-32.4	85.3	-32.3	14.0	-165.0		-8.4	21.7
CCSD(T)/aptz//MP2/apdz	47.8	2.0	115.2	-18.3	18.4	-142.3		15.4	23.8
CCSD(T)/apqz//MP2/apdz
B3LYP/apdz	23.2	-13.8	113.8	-34.5	17.7	-165.9	23.5	-4.1	37.4
B3LYP/aptz	85.8	3.1	129.6	-23.8	20.8	-151.4	28.7	10.8	43.9
MPW1PW91/apdz	25.1	-22.8	116.3	-33.5	19.8	-170.3	25.3	-3.2	42.7
MPW1PW91/aptz	32.8	-4.8	133.4	-22.2	23.2	-154.8	31.1	12.3	49.9

ArNOF	triplet state	Ar+N(Q)+ O(T)+F	Ar+N(D)+O(S)+F	ArO+ NF	TS	ArF(D) + NO(D)	TS	ArN(D) + OF(D)	TS
MP2/apdz	29.2	-148.6	-2.2	-113.9	17.4		21.5		42.3
MP2/aptz		-100.9	40.5		23.0		41.0		42.0
MP2/aptz//MP2/apdz		-103.6	37.8	-86.8	23.2
CCSD/aptz//MP2/apdz		-142.2	-20.8	-117.0	4.7
CCSD(T)/aptz//MP2/apdz		-109.8	3.4	-98.0	-0.4
B3LYP/apdz		-108.0	19.6	-102.4	4.2		16.3		15.2
B3LYP/aptz		-92.6	33.9	-91.4	6.3		23.0		19.2

KrNOF	triplet state	Kr+N(Q)+ O(T)+F	Kr+N(D)+O(S)+F	KrO+ NF	TS	KrF(D) + NO(D)	TS	KrN(D) + OF(D)	TS
MP2/apdz	62.5	-79.9	66.5	-60.1	31.3				58.1
MP2/aptz//MP2/apdz	64.9	-43.8	97.5	-43.6	34.9
CCSD/aptz//MP2/apdz	35.9	-90.0	31.4	-77.4	12.3
CCSD(T)/aptz//MP2/apdz	47.5	-59.2	54.0	-60.6	8.9

(2) XeNO₂^- and KrNO₂^-

Table 3.Calculated Bond Lengths (Å) and Bond Angles (º) of XeNO₂^-、ArNO₂^-and KrNO₂^-

		XeNO₂^-
Method	Xe-N	Xe-O	N-Xe-O	O-Xe-O
MP2/apdz	1.798	1.866	113.9	100.5
MP2/aptz	1.780	1.825	112.4	100.9
CCSD/aptz	1.801	1.830	112.9	101.1
CCSD(T)/aptz	1.825	1.860	113.2	101.9
BD(T)/aptz	1.823	1.859	113.2	101.9
B3LYP/apdz	1.862	1.919	114.9	102.5
B3LYP/aptz	1.825	1.868	113.4	102.6
MPW1PW91/apdz	1.838	1.890	114.6	101.9
MPW1PW91/aptz	1.804	1.840	113.1	102.1

		ArNO₂^-
Method	Ar-N	Ar-O	N-Ar-O	O-Ar-O
MP2/apdz	1.491	1.672	116.9	99.6

		KrNO₂^-
Method	Kr-N	Kr-O	N-Kr-O	O-Kr-O
MP2/apdz	1.620	1.732	115.1	100.2

Table 4.Calculated Energies (kcal/mol) Relative to XeNO₂^- 、ArNO₂^-and KrNO₂^-

XeNO₂^-	triplet state	Xe + N(Q) + O(T) + O-(D) rel.	Xe + N(D) + O(S) +O-(D) rel.	Xe + N(D) + O2- (D) rel.	XeO2 + N- (S) rel.	XeO + NO- rel.	TS	Xe + NO2- rel.
MP2/apdz	90.4	19.2	165.6	3.6	127.2	-45.4	46.2	-219.8
MP2/aptz	98.5	63.5	204.9	37.7	138.8	-23.2	47.9	-190.7
MP2/aptz//MP2/apdz	91.4	61.9	203.2	36.1	138.5	-24.1	47.3	-192.2
CCSD/apdz//MP2/apdz	67.2	-23.2	102.4	-34.2	93.9	-68.9	44.1	-230.9
CCSD/aptz//MP2/apdz	67.1	12.0	133.5	-7.6	103.8	-50.9	46.4	-208.3
CCSD/aptz	73.7	12.8	134.3	-7.2	104.5	-50.4		-208.3
CCSD(T)/apdz//MP2/apdz	72.2	1.0	118.7	-18.6	102.6	-56.3	39.9	-218.7
CCSD(T)/aptz//MP2/apdz	72.7	40.5	153.7	10.6	113.6	-37.1	41.9	-194.7
CCSD(T)/apqz//MP2/apdz	72.1	49.9	161.8	17.1	116.8	-33.4	41.8	-191.2
CCSD(T)/apqz//CCSD(T)/aptz		50.1	161.9	17.1
CCSD(T)/aptz		40.9	154.1	10.9	113.8	-36.8		-194.5
BD(T)/aptz	70.0	40.7	154.0	10.8	113.8	-36.6		-194.4
B3LYP/apdz	43.9	12.4	140.0	-20.1	102.3	-65.1	36.7	-230.2
B3LYP/aptz	57.4	32.5	159.0	-1.2	109.3	-51.1	43.9	-211.7
MPW1PW91/apdz	49.9	9.0	148.0	-16.0	109.1	-62.1	40.8	-232.1
MPW1PW91/aptz	64.1	30.9	169.1	4.6	117.1	-46.6	48.5	-211.9

ArNO₂^-	triplet state	Ar+N(Q)+O(T)+O-	Ar+N(D)+O(S)+O-	Ar + N(D) + O2- (D)	ArO2+N-(T)	ArO + NO-	TS	Ar +NO2-
MP2/apdz		-90.7	123.7	-135.6		-149.8		-359.0

KrNO₂^-	triplet state	Kr + N(Q) + O(T) + O-	Kr + N(D) + O(S) + O-	Kr + N(D) + O2- (D)	KrO2+N-(S)	KrO + NO-	TS	Kr+NO2-
MP2/apdz	88.1	-48.5	97.9	-64.2	105.6	-93.3	44.3	-287.5
MP2/aptz//MP2/apdz	90.6	-9.6	131.8	-35.4	116.0	-73.9	47.4	-263.6
CCSD/aptz//MP2/apdz	70.6	-52.3	69.1	-71.9	82.6	-97.1	42.0	-272.7
CCSD(T)/aptz//MP2/apdz	75.6	-24.9	88.3	-54.8	92.2	-83.6	35.5	-260.1

(3) XeF₂NO^-、ArF₂NO^-and KrF₂NO^-

Table 5.Calculated Bond Lengths (Å) and Bond Angles (º) of XeF₂NO^-、ArF₂NO^-and KrF₂NO^-

Cs			XeF₂NO^-
Method	Xe-N	Xe-F	Xe-O	N-Xe-O	N-Xe-F	F-Xe-O	F-Xe-F
MP2/apdz	1.797	2.160	1.820	117.9	98.1	96.1	152.0
MP2/aptz	1.771	2.131	1.789	113.9	99.6	95.6	151.5
CCSD/aptz	1.766	2.097	1.795	112.4	102.3	91.5	151.9
B3LYP/apdz	1.823	2.207	1.875	114.7	103.4	94.3	145.2
B3LYP/aptz	1.792	2.168	1.830	112.4	103.3	94.2	146.5
MPW1PW91/apdz	1.803	2.162	1.850	114.8	102.6	92.9	148.7
MPW1PW91/aptz	1.773	2.124	1.806	112.6	102.5	92.8	149.9

			ArF₂NO^-
Method	Ar-N	Ar-F	Ar-O	N-Ar-O	N-Xe-F	F-Ar-O	F-Ar-F
MP2/apdz	1.466	1.999	1.503	120.1	104.0	95.2	139.7

			KrF₂NO^-
Method	Kr-N	Kr-O	Kr-F	N-Kr-O	N-Kr-F	O-Kr-F
MP2/apdz	1.620	1.641	2.035	120.9	99.1	94.8

Table 6.Calculated Energies (kcal/mol) Relative to XeF₂NO^-、ArF₂NO^-and KrF₂NO^-

XeF₂NO^-	triplet state	Xe + F + F- + N(Q) + O(T)	Xe + 2F +N(Q) + O-(D)	Xe + F + F- +N(D) + O (S) rel.	FXeO- + NF rel.	TS	XeF2 + NO- (S)	TS	XeO + F2 + N-(S)	Xe + NO- +F2	Xe + NF + OF-
MP2/apdz	81.6	57.3	109.7	203.7	10.1	50.0	-39.2	53.6	184.7	-9.9	21.5
MP2/aptz	86.7	96.9	148.2	238.2	26.1	52.2	-20.1	49.5	200.6	11.7	44.7
MP2/aptz//MP2/apdz	81.6	95.6	146.9	236.9	25.4	52.0	-20.9	48.6	200.1	10.8	43.7
CCSD/apdz//MP2/apdz	57.5	7.9	55.0	133.5	-22.5	24.7	-62.2	50.3	137.7	-41.8	-19.9
CCSD/aptz//MP2/apdz	56.4	38.8	84.2	160.3	-10.4	27.6	-47.6	48.0	149.6	-25.7	-2.6
CCSD/aptz	67.3	41.8	87.2	163.2	-7.7		-46.0		152.1	-23.4	0.3
CCSD(T)/apdz//MP2/apdz	66.8	34.0	81.0	151.7	-10.0	23.5	-50.6	46.8	151.0	-27.9	-5.3
CCSD(T)/aptz//MP2/apdz	66.3	69.8	115.4	183.0	3.6	26.8	-34.7	44.7	164.8	-10.0	14.5
CCSD(T)/apqz//MP2/apdz	65.8	79.3	124.9	191.1	7.0	27.8	-31.5	43.5	170.3	-5.1	19.7
B3LYP/apdz	47.2	51.8	95.3	179.4	-13.8	18.9	-57.8	43.9	152.8	-33.3	-10.4
B3LYP/aptz	55.5	71.0	113.7	197.5	-0.9	22.8	-45.6	48.3	164.1	-18.3	5.9
MPW1PW91/apdz	52.1	45.5	89.4	184.5	-12.0	22.0	-56.7	47.8	159.1	-31.9	-6.9
MPW1PW91/aptz	61.0	65.8	108.8	204.0	1.4	26.4	-43.2	52.3	170.6	-16.5	10.2

ArF₂NO^-	triplet state	Ar+ F + F- + N(Q) + O(T)	Ar + 2F +N(Q) + O-(D)	Ar + F + F- +N(D) + O (S)	FArO- + NF	TS	ArF2 + NO- (S)	TS	ArO + F2 + N-(S)	Ar + NO- +F2	Ar + NF + OF-
MP2/apdz		-103.0	-50.6	43.4	-96.8	11.3			59.2	-170.2	-138.8
MP2/aptz//MP2/apdz		-57.8	-6.6	83.5	-72.2	15.5			84.9	-142.7	-109.8
CCSD/aptz//MP2/apdz		-96.6	-51.2	24.9	-97.9	1.2			44.9	-161.1	-138.0
CCSD(T)/aptz//MP2/apdz		-64.8	-19.2	48.4	-82.1	0.9			62.3	-144.5	-120.1

KrF₂NO^-	triplet state	Kr + F + F- +N(Q) + O (T)	Xe + 2F +N(Q) + O-(D) rel.	Kr + F + F- +N(D) + O (S)	rel. FKrO- + NF	TS	rel. KrF2 + NO- (S)	TS	KrO + F2 + N-(S)	Kr + NF + OF-	Kr + NO- +F2
MP2/apdz	68.7	-20.4	32.1	126.1	-38.6	31.1	-78.6		126.9	-56.1	-87.5
MP2/aptz//MP2/apdz	70.4	16.0	67.3	157.3	-23.5	33.7	-61.3		142.1	-35.9	-68.8
CCSD/aptz//MP2/apdz	48.8	-36.4	9.0	85.0	-58.6	11.5	-80.3		92.5	-77.8	-100.9
CCSD(T)/aptz//MP2/apdz	59.3	-5.1	40.6	108.2	-43.8	11.5	-69.9		108.9	-60.3	-84.8

(4) XeNO₂ F and KrNO₂F

Table 7.Calculated Bond Lengths (Å) and Bond Angles (º) of XeNO₂F and KrNO₂F

			XeNO₂F
Method	Xe-N	Xe-F	Xe-O	N-Xe-O	N-Xe-F	O-Xe-O
MP2/apdz	1.797	1.982	1.784	124.1	103.9	104.2
MP2/aptz	1.773	1.942	1.755	123.5	105.5	105.2
CCSD/aptz	1.769	1.910	1.762	121.9	110.0	107.1
B3LYP/apdz	1.819	2.026	1.837	121.9	109.7	106.8
B3LYP/aptz	1.792	1.979	1.793	121.4	110.0	106.9
MPW1PW91/apdz	1.798	1.991	1.814	121.9	109.8	106.9
MPW1PW91/aptz	1.771	1.942	1.771	121.5	110.0	106.9

			KrNO₂F
Method	Kr-N	Kr-O	Kr-F	N-Kr-O	N-Kr-F	O-Kr-O
MP2/apdz	1.606	1.617	1.869	123.4	103.8	104.4

Table 8.Calculated Energies (kcal/mol) Relative to XeNO₂F and KrNO₂ F

XeNO₂F	triplet state	rel. Xe +N(Q) + O (T) + O (T) + F	rel. Xe +N(D) + O (S) + O (S) + F	rel. FXeN + O2(S)	TS	rel. XeO2 + NF	TS	rel. XeO + NF + O (S)	rel. XeO + NO + F (D)	TS
MP2/apdz	58.9	1.4	215.7	-39.4		-0.4	51.6	69.4	-120.9
MP2/aptz	63.0	55.3	262.7	-15.2		14.1	53.7	99.2	-90.3
MP2/aptz//MP2/apdz	57.6	53.6	261.0	-16.0		13.9	54.0	98.2	-91.2
CCSD/apdz//MP2/apdz	44.4	-59.9	122.2	-56.9		-37.9	23.3	8.4	-159.4
CCSD/aptz//MP2/apdz	42.5	-17.5	159.3	-36.0		-25.7	25.8	32.4	-135.7
CCSD/aptz		-15.1	161.7	-47.0		-23.5		34.7	-133.3
CCSD(T)/apdz//MP2/apdz	46.6	-27.0	142.9	-50.4		-25.0	22.9	25.3	-137.7
CCSD(T)/aptz//MP2/apdz	45.7	21.6	185.6	-28.9		-11.3	27.1	52.1	-111.3
CCSD(T)/apqz//MP2/apdz		33.9	196.1	-24.1		-7.6		58.8	-105.7
B3LYP/apdz	26.4	-9.7	181.5	-65.9	21.1	-33.3	20.7	33.3	-146.0
B3LYP/aptz	32.3	16.9	206.8	-44.7		-20.7	23.8	53.4	-126.3
MPW1PW91/apdz	31.7	-18.0	189.7	-61.2		-29.8	23.7	39.9	-146.8
MPW1PW91/aptz	38.2	10.5	217.6	-38.2		-16.1	27.2	61.9	-125.3

KrNO₂F	triplet state	Kr +N(Q) + O (T) + O (T) + F	Kr +N(D) + O (S) + O (S) + F	FKrN + O2(S)	TS	rel. KrO2 + NF	TS	KrO + NF + O (S)	KrO + NO + F (D)	TS
MP2/apdz		-84.4	130.0	-89.4		-40.0	50.3	3.4	-186.8
MP2/aptz//MP2/apdz		-34.8	172.7	-66.0		-25.4	52.8	31.5	-158.0
CCSD/aptz//MP2/apdz		-102.5	74.3	-90.1		-67.6	26.0	-34.5	-202.5
CCSD(T)/aptz//MP2/apdz		-63.9	100.1	-84.9		-52.9	23.0	-14.5	-177.9