红移: 由于取代基作用或溶剂效应导致生色基的吸收峰向长波移动的现象称为红移。 — 红移一般是由于共轭体系延长或增加了助色基引起。

基本原理: 紫外光谱是由样品分子吸收一定波长的光，使其电子从基态跃迁到激发态引起。

紫外光谱的产生: 1.几乎所有的有机分子的紫外-可见吸收光谱都是由于π→π*或n→π*跃迁所产生的; 2.含S、I等元素时的n→σ*; 3.电荷转移跃迁; 4.配位体场的d→d*跃迁产生。

生色基也称发色基(团) : 是指分子中某一基团或体系，由于其存在能使分子产生吸收而出现谱带,这一基团或体系即为生色基。

助色基(团): 是指在紫外-可见光区内不一定发生吸收。但当它与生色基相连时能使生色基的吸收谱带明显地向长波移动，而且吸收强度也相应的增加。

蓝移(紫移) :生色基吸收峰向短波方向的移动称为紫移或蓝移。 增色效应:使吸收带强度增加的作用称为增色效应 减色效应:使吸收带的强度降低的作用称为减色效应。

R带: 为n→π*跃迁引起的吸收带，产生该吸收的生色基是分子中的p-π共轭，如-C=O, -NO, -CHO等。

K带: 由π-→π* 跃迁引起的吸收带，产生该吸收带的发色团是分子中共轭系统。

B带和E带均为芳香化合物的π→π*吸收带。苯环有三个π→π* 跃迁的吸收峰，即一个B带和两个E带。

B带:由苯的π→π* 跃迁和振动效应的重叠引起，为一宽峰并出现若干小峰，在230~270nm之间，中心在254 nm处，εmax≈250左右。是苯环的特征峰。 苯环被取代后，精细结构消失或部分消失。B带常用来识别芳香族化合物

紫外光谱谱带有: B带:ε值约250~3000 E带:ε值约2000 ~ 10000 K带ε值约10000 (或大于10000) R带:ε值<100

特点： 1、分析速度快 2、光谱数据积累较多 3、红外吸收只有振-转跃迁，能量低 4、应用范围广:几乎所有有机物均有红外吸收 5、固、液、气态样均可用，用量少、不破坏样品 6、与色谱联用具有强大的定性功能

产生的条件： 条件一:辐射光子的能量应与振动跃迁所需能量相等。 根据量子力学原理，分子振动能量Ev是量子化的,即Ev= (V+1/2) hv “v-振动频率” “V-振动量子数，值取0，1, 2，...” 只有当Ea=△Ev时，才可能发生振转跃迁。 相邻两个能级间的能量差ΔEv= hv

多原子分子振动光谱： N个原子组成的分子，每个原子在空间的位置要有三个坐标，由N个原子组成的分子就需要3N个坐标，也就是有3N个运动自由度。 3N=平动+转动+振动 振动自由度=3N-6一 非线性分子 振动自由度=3N-5一 线性分子

(1)峰位 ： 化学键的力常数k越大， 原子折合质量越小， 键的振动频率越大， 吸收峰将出现在高波数区; 反之，出现在低波数区。

基频峰： 分子吸收一定频率的红外光后，振动能级从基态跃迁到第一激发态 (Vo→V1)时所产生的吸收。 倍频峰： 振动能级从基态跃迁到第二(V2)、第三(V3)...激发态所产生的吸收。 组频峰(包括合频峰和差频峰)。 倍频峰和组频峰总称为泛频峰。

特征峰： 凡能用于鉴定原子基团存在并有较高强度的吸收峰一特征峰。 其对应的频率称为特征频率。 相关峰： 一个基团除了特征峰以外，还有许多其它振动形式的吸收峰，这些相互依存而又相互可以佐证的吸收峰

谱带的强度主要由两个因素决定: (1)是跃迁的几率。跃迁的几率大，吸收峰也就强。 跃迁的几率与振动方式有关: 基频(Vo- >V)跃迁几率大，所以吸收较强; 倍频(Vo-→V2)虽然偶极矩变化大，但跃率几率很低，使峰强反而很弱。

偶极矩变化的大小与以下四个因素有关: (1)化学键两端原子的电负性差越大，引起的红外吸收越强。 (2)振动方式。相同基团的振动方式不同，分子的电荷分布也不同，偶极矩变化也不同。 反对称伸缩振动比对称伸缩振动的吸收强度大; 伸缩振动的吸收强度比变形振动的吸收强度大。

(4)其他因素: (a)氢键的形成使有关的吸收峰变宽变强。 (b)与极性基团共轭使吸收峰增强。如C=C、C=C等基团的伸缩振动吸收很弱。但是，如果它们与C=O或C=N共轭，吸收强度会大大增强。

影响峰位置变化的因素 1、成键轨道类型:力常数sp> sp2 > sp3 2、诱导效应:由于邻近原子或基团的诱导效应的影响使基团中电荷分布发生变化，从而改变了键的力常数,使振动频率发生变化. 吸电子基团使吸收峰向高频方向移动(蓝移) 供电子基团使吸收峰向低频方向移动(红移)

5、氢键的影响：形成氢键后基团的伸缩频率都会下降。 6、振动的耦合：若分子内的两个基团位置很近，振动频率也相近，就可能发生振动耦合，使谱带分成两个，在原谱带高频和低频一侧各出现一个谱带。（弯曲振动也能发生耦合。）

外分光光度计(按分光器将红外分光光度计分为四代): 以人工晶体棱镜作为色散元件的第一代; 以光栅作为分光元件的第二代; 以干涉仪为分光器的傅里叶变换红外光度计是第三代; 用可调激光光源的第四代仪器。

傅里叶变换红外分光光度计还具有以下特点: (1)分辨率高，可达0.lcm-1, 波数准确度高达0.0lcm-1。 (2)扫描时间短，在几十分之-秒内可扫描一次。可用于快速化学反应的追踪、研究瞬间的变化、解决气相色谱和红外的联用问题。 (3)FTIR不用狭缝，消除了狭缝对光谱能量的限制，使光能的利用率大大提高。

红外显微镜: 可将光聚集在一个很小的区域，故可对样品的局部进行分析，可用于实际工作中一些特殊固体样品的分析检测。

固体样品的制样方法: (1)压片法:取1~3mg试样，加100~300mg处理过的KBr研细，使粒度小于2.5um,形成一个薄片，外观上透明。 适用于可以研细的固体样品。 但对不稳定的化合物，易分解、异构化、升华等的化合物则不宜使用压片法。 样品可以回收。KBr易吸收水份，要避免水份的影响。

(3)溶液法:将固体样品溶解在溶剂中，注入液体池测定。 在溶剂吸收特别强的区域光能几乎被溶剂全部吸收，形成了所谓的“死区 ，谱线在此区域为平坦的曲线，所以在选择溶剂时不要让观察的吸收峰落入“死区” 。

(4)薄膜法: 一些高分子膜常常可以直接用来测试，而更多的情况是要将样品制成膜。 (5)全反射光谱测定法(ATR)： 一些不溶、不熔且难粉碎的片状试样及不透明表面的涂层可以采用此法测定。

液体样品的制样法： (1)溶液法 (2)液膜法:成一层薄的液膜用于测定。此方法只适用于高沸点液体化合物。

制样时要注意的问题： (1) 首先要了解样品纯度。一般要求样品纯。对含水份和溶剂的样品要作干燥处理。 (2)根据样品的物态和理化性质选择制样方法。如果样品不稳定，则应避免使用压片法。 (3)制样过程要注意避免空气中水份、CO2等污染物混入样品。

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